JP2020139015A - Moisturizing agent polymer - Google Patents
Moisturizing agent polymer Download PDFInfo
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- JP2020139015A JP2020139015A JP2019034270A JP2019034270A JP2020139015A JP 2020139015 A JP2020139015 A JP 2020139015A JP 2019034270 A JP2019034270 A JP 2019034270A JP 2019034270 A JP2019034270 A JP 2019034270A JP 2020139015 A JP2020139015 A JP 2020139015A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 103
- 230000003020 moisturizing effect Effects 0.000 title abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 97
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- 239000004909 Moisturizer Substances 0.000 claims description 99
- 230000001333 moisturizer Effects 0.000 claims description 99
- 125000004432 carbon atom Chemical group C* 0.000 claims description 75
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- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- 125000004429 atom Chemical group 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 32
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- 125000001424 substituent group Chemical group 0.000 claims description 26
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- SJOXEWUZWQYCGL-UHFFFAOYSA-N salicylic acid menthyl ester Natural products CC(C)C1CCC(C)CC1OC(=O)C1=CC=CC=C1O SJOXEWUZWQYCGL-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 239000008257 shaving cream Substances 0.000 description 1
- 229940057910 shea butter Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- LLELVHKMCSBMCX-UHFFFAOYSA-M sodium 1-[(4-chloro-5-methyl-2-sulfophenyl)diazenyl]naphthalen-2-olate Chemical compound [Na+].Cc1cc(N=Nc2c(O)ccc3ccccc23)c(cc1Cl)S([O-])(=O)=O LLELVHKMCSBMCX-UHFFFAOYSA-M 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 1
- JAOZKJMVYIWLKU-UHFFFAOYSA-N sodium 7-hydroxy-8-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1=CC=C2C(=C1)C(=CC=C2S(=O)(=O)O)N=NC3=C(C=CC4=CC(=CC(=C43)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] JAOZKJMVYIWLKU-UHFFFAOYSA-N 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940096501 sodium cocoamphoacetate Drugs 0.000 description 1
- 229940079781 sodium cocoyl glutamate Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
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- 229940045944 sodium lauroyl glutamate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
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- IWIUXJGIDSGWDN-UQKRIMTDSA-M sodium;(2s)-2-(dodecanoylamino)pentanedioate;hydron Chemical compound [Na+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC(O)=O IWIUXJGIDSGWDN-UQKRIMTDSA-M 0.000 description 1
- KDHFCTLPQJQDQI-BDQAORGHSA-M sodium;(4s)-4-amino-5-octadecanoyloxy-5-oxopentanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC(=O)OC(=O)[C@@H](N)CCC([O-])=O KDHFCTLPQJQDQI-BDQAORGHSA-M 0.000 description 1
- PWZDAQKVUDZPRI-LMOVPXPDSA-M sodium;(4s)-4-amino-5-oxo-5-tetradecoxypentanoate Chemical compound [Na+].CCCCCCCCCCCCCCOC(=O)[C@@H](N)CCC([O-])=O PWZDAQKVUDZPRI-LMOVPXPDSA-M 0.000 description 1
- GOJYXPWOUJYXJC-UHFFFAOYSA-M sodium;2-[1-(2-hydroxyethyl)-2-undecyl-4,5-dihydroimidazol-1-ium-1-yl]acetate;hydroxide Chemical compound [OH-].[Na+].CCCCCCCCCCCC1=NCC[N+]1(CCO)CC([O-])=O GOJYXPWOUJYXJC-UHFFFAOYSA-M 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
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- 210000001913 submandibular gland Anatomy 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- GYDJEQRTZSCIOI-LJGSYFOKSA-N tranexamic acid Chemical compound NC[C@H]1CC[C@H](C(O)=O)CC1 GYDJEQRTZSCIOI-LJGSYFOKSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
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- PMBRBOODEWULOI-UHFFFAOYSA-N trichloromethanide Chemical compound Cl[C-](Cl)Cl PMBRBOODEWULOI-UHFFFAOYSA-N 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- LINXHFKHZLOLEI-UHFFFAOYSA-N trimethyl-[phenyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 LINXHFKHZLOLEI-UHFFFAOYSA-N 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- ZDPHROOEEOARMN-UHFFFAOYSA-M undecanoate Chemical compound CCCCCCCCCCC([O-])=O ZDPHROOEEOARMN-UHFFFAOYSA-M 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- LLWJPGAKXJBKKA-UHFFFAOYSA-N victoria blue B Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=CC=C1 LLWJPGAKXJBKKA-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 239000001717 vitis vinifera seed extract Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000009538 yokuinin Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229960001296 zinc oxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- ZNVKGUVDRSSWHV-UHFFFAOYSA-L zinc;4-hydroxybenzenesulfonate Chemical compound [Zn+2].OC1=CC=C(S([O-])(=O)=O)C=C1.OC1=CC=C(S([O-])(=O)=O)C=C1 ZNVKGUVDRSSWHV-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、保湿剤用ポリマーに関する。より詳しくは、保湿剤、皮膚化粧料、皮膚外用剤、頭髪化粧料などに有用な、保湿剤用ポリマーに関する。 The present invention relates to polymers for moisturizers. More specifically, the present invention relates to a polymer for a moisturizer, which is useful for a moisturizer, a skin cosmetic, an external preparation for the skin, a hair cosmetic, and the like.
化粧品には皮膚の乾燥を防ぐために保湿剤が配合されている。従来の保湿剤としては、グリセリンや1,3−ブタンジオールなどの多価アルコール、ヒアルロン酸Naなどが知られている。 Cosmetics contain moisturizers to prevent the skin from drying out. As conventional moisturizers, polyhydric alcohols such as glycerin and 1,3-butanediol, and sodium hyaluronate are known.
従来の保湿剤として、高分子が肌表面に被膜を形成することにより水分の蒸発を抑制する、被膜形成型高分子型保湿剤も提案されている。例えば、アミド基を含有する特定の単位構造を有する親水性高分子(特許文献1)、特定の構造単位を有し、重量平均分子量(Mw)が5,000〜150,000であり、温度30℃、相対湿度60%における当該ポリマーの50質量%水溶液の6時間放置後の質量減少率が25質量%以下である化粧料または皮膚外用剤用の水溶性(メタ)アクリルアミドポリマー(特許文献2)、ビニルピロリドンを構成単位として含む共重合体からなる両親媒性高分子化合物(A)と、ビワ葉エキス(B)をエキス純分(B’)として0.001質量%〜0.02質量%とダイズエキス(C)(エキス純分(C’))とを含有してなり、(A)/[(B’)+(C’)]で表される含有質量比が1〜1000である化粧料(特許文献3)が提案されている。 As a conventional moisturizer, a film-forming polymer-type moisturizer that suppresses the evaporation of water by forming a film on the skin surface by the polymer has also been proposed. For example, a hydrophilic polymer having a specific unit structure containing an amide group (Patent Document 1), having a specific structural unit, having a weight average molecular weight (Mw) of 5,000 to 150,000, and having a temperature of 30. A water-soluble (meth) acrylamide polymer for cosmetics or skin external preparations, which has a mass loss rate of 25% by mass or less after being left for 6 hours in a 50% by mass aqueous solution of the polymer at ° C. and 60% relative humidity (Patent Document 2). , 0.001% by mass to 0.02% by mass of an amphoteric polymer compound (A) composed of a polymer containing vinylpyrrolidone as a constituent unit and a biwa leaf extract (B) as an extract pure content (B'). And soybean extract (C) (pure extract (C')), and the content mass ratio represented by (A) / [(B') + (C')] is 1 to 1000. Fees (Patent Document 3) have been proposed.
しかしながら、従来のグリセリンや1,3−ブタンジオールなどの多価アルコールは、低湿度下では吸湿性が不足し、保湿性を十分に維持することができず、さらに、高湿度下では吸湿性が高すぎるために、べたつきが生じてしまうという問題がある。また、従来のヒアルロン酸Naは非常に高価であるという問題や、超高分子量のために系全体が増粘することから配合量に制限があるという問題がある。 However, conventional polyhydric alcohols such as glycerin and 1,3-butanediol have insufficient hygroscopicity under low humidity, cannot sufficiently maintain moisturizing property, and further have hygroscopicity under high humidity. There is a problem that stickiness occurs because it is too expensive. Further, there is a problem that the conventional Na hyaluronate is very expensive, and there is a problem that the blending amount is limited because the whole system is thickened due to the ultrahigh molecular weight.
また、特許文献1および特許文献2に記載の保湿剤は、保湿性に乏しく、特に、低湿度下における保湿性において改善の余地がある。さらに、特許文献3に記載の保湿剤は、ビワ葉エキスやダイズエキスと高分子型保湿剤とを併用しなければ、保湿効果が持続できないというものである。 Further, the moisturizers described in Patent Document 1 and Patent Document 2 are poor in moisturizing property, and there is room for improvement in moisturizing property under low humidity. Further, the moisturizer described in Patent Document 3 is such that the moisturizing effect cannot be maintained unless the loquat leaf extract or soybean extract and the polymer type moisturizer are used in combination.
最近、本出願人は、保湿性能に優れた化合物について種々検討し、ラクタム構造を有する不飽和単量体由来の構造単位と特定の官能基を有する不飽和単量体由来の構造単位とを有するポリマーがその他の保湿成分を添加しない場合でも、単独でも優れた保湿性能を発揮し、低湿度下での保湿性の維持にも優れること、および、このポリマーがヒアルロン酸Naより安価に製造可能であることを報告している(特許文献4)。 Recently, the applicant has studied various compounds having excellent moisturizing performance, and has a structural unit derived from an unsaturated polymer having a lactam structure and a structural unit derived from an unsaturated polymer having a specific functional group. Even when the polymer does not add other moisturizing ingredients, it exhibits excellent moisturizing performance by itself, is also excellent in maintaining moisturizing properties under low humidity, and this polymer can be produced at a lower cost than Na hyaluronate. It is reported that there is (Patent Document 4).
本出願人は、特許文献4で報告した保湿剤用ポリマーについて、さらに詳細に各種検討を重ねた。その結果、重量平均分子量を特定の範囲に制御した保湿剤用ポリマーが、保湿剤としたときの保湿性、塗布感触(弾力感)、残存感触(摩擦感、粘着感)に優れることを見出し、本発明を完成させるに至った。 The applicant has conducted various studies on the moisturizer polymer reported in Patent Document 4 in more detail. As a result, it was found that the polymer for a moisturizer in which the weight average molecular weight is controlled in a specific range is excellent in moisturizing property, application feel (elasticity), and residual feel (friction, adhesiveness) when used as a moisturizer. The present invention has been completed.
本発明の課題は、保湿剤としたときの保湿性、塗布感触(弾力感)、残存感触(摩擦感、粘着感)が優れる保湿剤用ポリマーを提供することにある。 An object of the present invention is to provide a polymer for a moisturizer, which is excellent in moisturizing property, coating feel (elasticity), and residual feel (friction, adhesiveness) when used as a moisturizer.
本発明の保湿剤用ポリマーは、
ラクタム構造を有する不飽和単量体(A)由来の構造単位(a)と、一般式(1)で表される不飽和単量体(B)由来の構造単位(b)とを有し、
重量平均分子量が80000以上である。
It has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure and a structural unit (b) derived from an unsaturated monomer (B) represented by the general formula (1).
The weight average molecular weight is 80,000 or more.
一つの実施形態においては、上記ラクタム構造を有する不飽和単量体(A)が、ピロリドン環を有する不飽和単量体である。 In one embodiment, the unsaturated monomer (A) having a lactam structure is an unsaturated monomer having a pyrrolidone ring.
一つの実施形態においては、不飽和単量体(B)が一般式(2)で表される。
一つの実施形態においては、上記構造単位(b)が、(メタ)アクリル酸またはこれらの塩、ポリアルキレングリコール含有単量体、水酸基含有単量体からなる群から選ばれる少なくとも1種由来の構造単位である。 In one embodiment, the structural unit (b) is a structure derived from at least one selected from the group consisting of (meth) acrylic acid or salts thereof, polyalkylene glycol-containing monomers, and hydroxyl group-containing monomers. It is a unit.
一つの実施形態においては、全構造単位100質量%に対する上記構造単位(a)の割合が30質量%〜99質量%である。 In one embodiment, the ratio of the structural unit (a) to 100% by mass of all structural units is 30% by mass to 99% by mass.
一つの実施形態においては、本発明の保湿剤用ポリマーは、水溶性である。 In one embodiment, the moisturizer polymer of the present invention is water soluble.
一つの実施形態においては、本発明の保湿剤用ポリマーは、保湿剤に用いられる。 In one embodiment, the moisturizer polymer of the present invention is used as a moisturizer.
一つの実施形態においては、本発明の保湿剤用ポリマーは、皮膚化粧料、皮膚外用剤、または頭髪化粧料に用いられる。 In one embodiment, the moisturizer polymer of the present invention is used in skin cosmetics, external skin preparations, or hair cosmetics.
本発明の保湿剤は、本発明の保湿剤用ポリマーを含む。 The moisturizer of the present invention includes the polymer for the moisturizer of the present invention.
本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料は、本発明の保湿剤用ポリマーを含む。 The skin cosmetics, external preparations for skin, or hair cosmetics of the present invention include the polymer for moisturizers of the present invention.
本発明によれば、保湿剤としたときの保湿性、塗布感触(弾力感)、残存感触(摩擦感、粘着感)が優れる保湿剤用ポリマーを提供することができる。 According to the present invention, it is possible to provide a polymer for a moisturizer having excellent moisturizing properties, a coating feel (elasticity), and a residual feel (friction, stickiness) when used as a moisturizer.
本明細書中で「質量」との表現がある場合は、従来一般に重さの単位として慣用されている「重量」と読み替えてもよく、逆に、本明細書中で「重量」との表現がある場合は、重さを示すSI系単位として慣用されている「質量」と読み替えてもよい。 When the expression "mass" is used in the present specification, it may be read as "weight" which is generally used as a unit of weight in the past, and conversely, the expression "weight" in the present specification. If there is, it may be read as "mass" which is commonly used as an SI unit indicating weight.
本明細書中で「単量体(P)由来の構造単位」(Pは任意の適切な符号を表し、(P)の表記はない場合もある)とは、代表的には、「単量体(P)」(または単に「単量体」)が有する重合性不飽和二重結合が、重合によって結合の一つが開き、重合体の少なくとも一部を構成する単位(Q)(Qは任意の適切な符号を表し、(Q)の表記はない場合もある)となったものを意味する。具体的には、下記の一般式(P)で表される単量体(P)由来の構造単位が一般式(Q)で表される構造単位である。なお、上記「単量体(P)由来の構造単位」には、上記のように単量体(P)(または単に「単量体」)が重合して形成される構造単位(下記に示す具体例では一般式(Q)で表される構造単位)と同じ構造であれば、別の製法によって形成された構造単位であってもよい。 In the present specification, "structural unit derived from monomer (P)" (P represents an arbitrary appropriate code and may not be represented by (P)) is typically referred to as "single amount". The polymerizable unsaturated double bond of the "form (P)" (or simply "monomer") is a unit (Q) (Q is arbitrary) in which one of the bonds is opened by polymerization and constitutes at least a part of the polymer. Represents an appropriate code of (Q) may not be indicated). Specifically, the structural unit derived from the monomer (P) represented by the following general formula (P) is the structural unit represented by the general formula (Q). The "structural unit derived from the monomer (P)" is a structural unit (shown below) formed by polymerizing the monomer (P) (or simply the "monomer") as described above. In a specific example, the structural unit may be formed by another manufacturing method as long as it has the same structure as the structural unit represented by the general formula (Q).
以下において記載する本発明の個々の好ましい形態を2つ以上組み合わせたものも、また、本発明の好ましい形態である。 A combination of two or more of the individual preferred embodiments of the invention described below is also a preferred embodiment of the invention.
≪保湿剤用ポリマー≫
本発明の保湿剤用ポリマーは、ラクタム構造を有する不飽和単量体(A)由来の構造単位(a)と、一般式(1)で表される不飽和単量体(B)由来の構造単位(b)とを有する。本発明の保湿剤用ポリマーがこのような構造を有することにより、単独でも優れた保湿性能を発揮し、低湿度下での保湿性の維持にも優れる。また、本発明の保湿剤用ポリマーは、親水性と親油性とのバランスに優れているため、高湿度下における吸湿性が小さく、化粧品等に用いた場合に高湿度下でのべたつきを抑制することができる。なお、ラクタム構造を有する不飽和単量体(A)、ラクタム構造を有する不飽和単量体(A)由来の構造単位(a)、一般式(1)で表される不飽和単量体(B)、一般式(1)で表される不飽和単量体(B)由来の構造単位(b)は、それぞれ、1種のみであってもよいし、2種以上であってもよい。
≪Polymer for moisturizer≫
The polymer for a moisturizer of the present invention has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure and a structure derived from an unsaturated monomer (B) represented by the general formula (1). It has a unit (b). Since the polymer for a moisturizer of the present invention has such a structure, it exhibits excellent moisturizing performance by itself and is also excellent in maintaining moisturizing properties under low humidity. Further, since the polymer for a moisturizer of the present invention has an excellent balance between hydrophilicity and lipophilicity, it has low hygroscopicity under high humidity and suppresses stickiness under high humidity when used in cosmetics and the like. be able to. The unsaturated monomer (A) having a lactam structure, the structural unit (a) derived from the unsaturated monomer (A) having a lactam structure, and the unsaturated monomer represented by the general formula (1) ( The structural unit (b) derived from the unsaturated monomer (B) represented by B) and the general formula (1) may be only one type or two or more types, respectively.
本発明の保湿剤用ポリマーは、重量平均分子量が80000以上であり、好ましくは100000〜1000000であり、より好ましくは100000〜800000であり、さらに好ましくは100000〜500000であり、さらに好ましくは100000〜300000であり、特に好ましくは100000〜250000であり、最も好ましくは100000〜200000である。本発明の保湿剤用ポリマーは、重量平均分子量がこのような狭い範囲に調整されたことにより、保湿剤としたときの保湿性、塗布感触(弾力感)、残存感触(摩擦感、粘着感)が優れる。塗布感触(弾力感)、残存感触(摩擦感、粘着感)の評価については、後で詳述する。 The moisturizer polymer of the present invention has a weight average molecular weight of 80,000 or more, preferably 100,000 to 1,000,000, more preferably 100,000 to 800,000, still more preferably 100,000 to 500,000, still more preferably 100,000 to 300,000. It is particularly preferably 100,000 to 250,000, and most preferably 100,000 to 200,000. The polymer for a moisturizer of the present invention has a weight average molecular weight adjusted to such a narrow range, so that the moisturizer has moisturizing properties, a coating feel (elasticity), and a residual feel (friction, adhesiveness). Is excellent. The evaluation of the applied feel (elasticity) and the residual feel (friction, adhesiveness) will be described in detail later.
本発明の保湿剤用ポリマーは、一般式(1)で表される不飽和単量体(B)由来の構造単位(b)を有する。 The polymer for a moisturizer of the present invention has a structural unit (b) derived from an unsaturated monomer (B) represented by the general formula (1).
一般式(1)中、R1、R2、R3は、同一または異なって、水素原子、水酸基、炭素数1〜10のアルキル基、−(CH2)zCOORp(−(CH2)zCOORpは、−COOR4またはその他の−(CH2)zCOORpと無水物を形成していてもよい)を表し、wは0〜2の整数を表し、zは0〜2の整数を表し、R4、Rpは、同一または異なって、水素原子、1価〜3価の金属原子、1価〜3価の金属原子を含む原子団、アンモニウム塩、第4級アンモニウム塩基、置換基を有していてもよい(ポリ)オキシアルキレン基、または置換基として水酸基、アルコキシ基、(ポリ)オキシアルキレン基、オキソ基含有基、ハロゲン原子、エポキシ基、およびカルボニル基からなる群より選択される少なくとも1種を有していてもよい炭素数1〜30の炭化水素基を表す。 In the general formula (1), R 1 , R 2 , and R 3 are the same or different, and have a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, and-(CH 2 ) zCOOR p (-(CH 2 ) zCOOR. p represents −COOR 4 or other − (CH 2 ) zCOOR p , which may form an anhydride), w represents an integer of 0-2, z represents an integer of 0-2, R 4, R p are the same or different, a hydrogen atom, a monovalent to trivalent metal atom, atomic group, an ammonium salt comprising a monovalent to trivalent metal atom, a quaternary ammonium base, have a substituent At least selected from the group consisting of a hydroxyl group, an alkoxy group, a (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, an epoxy group, and a carbonyl group as a (poly) oxyalkylene group or a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have one kind.
R1、R2、R3における炭素数1〜10のアルキル基は、好ましくは炭素数1〜5のアルキル基であり、より好ましくは炭素数1〜3のアルキル基である。このようなアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられ、好ましくは、メチル基、エチル基であり、より好ましくは、メチル基である。 The alkyl group having 1 to 10 carbon atoms in R 1 , R 2 and R 3 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group and a propyl group, preferably a methyl group and an ethyl group, and more preferably a methyl group.
R1、R2は、好ましくは、水素原子である。 R 1 and R 2 are preferably hydrogen atoms.
R3は、好ましくは、水素原子、水酸基、メチル基であり、より好ましくは、水素原子またはメチル基である。 R 3 is preferably a hydrogen atom, a hydroxyl group, or a methyl group, and more preferably a hydrogen atom or a methyl group.
wは、好ましくは0または1であり、より好ましくは0である。 w is preferably 0 or 1, more preferably 0.
R4、Rpにおける1価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な1価の金属原子を採用し得る。このような1価の金属原子としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属原子が挙げられ、好ましくは、ナトリウム、カリウムである。 The monovalent metal atom in R 4, R p, within the range not impairing the effects of the present invention may employ any suitable monovalent metal atom. Examples of such monovalent metal atoms include alkali metal atoms such as lithium, sodium and potassium, and sodium and potassium are preferable.
R4、Rpにおける2価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な2価の金属原子を採用し得る。このような2価の金属原子としては、例えば、カルシウム、マグネシウム等のアルカリ土類金属原子が挙げられる。 As the divalent metal atom in R 4 and R p , any appropriate divalent metal atom can be adopted as long as the effect of the present invention is not impaired. Examples of such divalent metal atoms include alkaline earth metal atoms such as calcium and magnesium.
R4、Rpにおける3価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な3価の金属原子を採用し得る。このような3価の金属原子としては、例えば、アルミニウム、鉄などが挙げられる。 Examples of the trivalent metal atoms in R 4, R p, within the range not impairing the effects of the present invention may employ any suitable trivalent metal atoms. Examples of such a trivalent metal atom include aluminum and iron.
R4、Rpにおける1価〜3価の金属原子を含む原子団としては、本発明の効果を損なわない範囲で、任意の適切な1価〜3価の金属原子を含む原子団を採用し得る。このような1価〜3価の金属原子を含む原子団としては、例えば、ジアンミン銀イオン、ビオレオ、テトラアンミン亜鉛(II)イオン、ヘキサアンミンニッケル(II)イオン、ヘキサアンミンクロム(III)イオン、ローゼオなどが挙げられる。 The atomic group containing a monovalent to trivalent metal atom in R 4, R p, within the range not impairing the effects of the present invention, employing an atomic group comprising any suitable monovalent to trivalent metal atom obtain. Examples of the atomic group containing such monovalent to trivalent metal atoms include diammine silver ion, violeo, tetraammine zinc (II) ion, hexaammine nickel (II) ion, hexaammine chromium (III) ion, and roseo. And so on.
R4、Rpにおける第4級アンモニウム塩基としては、本発明の効果を損なわない範囲で、任意の適切な三価の金属原子を採用し得る。このような第4級アンモニウム塩基としては、例えば、−+NR7 3で表される基が挙げられる。ここで、R7は、同一または異なって、水素原子または炭素数1〜6のアルキル基を表す。 The quaternary ammonium base in R 4, R p, within the range not impairing the effects of the present invention may employ any suitable trivalent metal atoms. Such quaternary ammonium bases, for example, - + NR 7 groups represented by 3 and the like. Here, R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which is the same or different.
R4、Rpにおける置換基を有していてもよい(ポリ)オキシアルキレン基としては、本発明の効果を損なわない範囲で、任意の適切な置換基を有していてもよい(ポリ)オキシアルキレン基を採用し得る。このような置換基を有していてもよい(ポリ)オキシアルキレン基としては、例えば、下記一般式(A)で表される基が挙げられる。 The R 4, which may have a substituent in R p (poly) oxyalkylene group, in a range that does not impair the effects of the present invention, may have any suitable substituent (poly) An oxyalkylene group can be adopted. Examples of the (poly) oxyalkylene group which may have such a substituent include a group represented by the following general formula (A).
一般式(A)中、Raは、炭素数2〜30のアルキレン基であり、Rbは、水素原子または置換基を有していてもよい炭素数1〜30の基であり、nは1〜200の数である。 In the general formula (A), Ra is an alkylene group having 2 to 30 carbon atoms, R b is a group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, and n is a group having 1 to 30 carbon atoms. It is a number from 1 to 200.
一般式(A)中のRbにおける炭素数1〜30の基としては、例えば、アルキル基、アリール基、アシル基、カルバモイル基、複素環基などが挙げられ、これらはさらに置換基を有していてもよい。 Examples of the group having 1 to 30 carbon atoms in R b in the general formula (A) include an alkyl group, an aryl group, an acyl group, a carbamoyl group, a heterocyclic group and the like, and these groups further have a substituent. May be.
一般式(A)中のRbは、炭素数が1〜18の基であることが好ましく、炭素数が1〜12の基であることがより好ましい。 R b in the general formula (A) is preferably a group having 1 to 18 carbon atoms, and more preferably a group having 1 to 12 carbon atoms.
一般式(A)中、Raは、−CH2CH2−基、−CH2CH2(CH3)−基、−CH2CH2(C2H5)−基からなる群から選ばれる少なくとも1種を含むことが好ましく、−CH2CH2−基、−CH2CH2(CH3)−基、−CH2CH2(C2H5)−基の合計のアルキレン基全体に占める割合が、50モル%以上であることが好ましく、80モル%以上であることがより好ましく、90モル%以上であることがさらに好ましい。一般式(A)中、Raは、−CH2CH2−基を含むことが好ましく、−CH2CH2−基がアルキレン基全体に占める割合が、50モル%以上であることが好ましく、80モル%以上であることがより好ましく、90モル%以上であることがさらに好ましい。 In the general formula (A), Ra is selected from the group consisting of -CH 2 CH 2 -group, -CH 2 CH 2 (CH 3 ) -group, and -CH 2 CH 2 (C 2 H 5 ) -group. It preferably contains at least one type, and accounts for the total alkylene group of −CH 2 CH 2 − group, −CH 2 CH 2 (CH 3 ) − group, and −CH 2 CH 2 (C 2 H 5 ) − group. The ratio is preferably 50 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. In the general formula (A), R a is, -CH 2 CH 2 - preferably comprises group, -CH 2 CH 2 - percentage of groups in the whole alkylene group, preferably at least 50 mol%, It is more preferably 80 mol% or more, and further preferably 90 mol% or more.
一般式(A)中、nは、1〜100の数であることが好ましく、1〜60の数であることがより好ましい。 In the general formula (A), n is preferably a number of 1 to 100, and more preferably a number of 1 to 60.
R4、Rpにおける炭素数1〜30の炭化水素基としては、本発明の効果を損なわない範囲で、任意の適切な炭素数1〜30の炭化水素基を採用し得る。このような炭素数1〜30の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基等の炭素数1〜30のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数3〜30のシクロアルキル基;フェニル基、ベンジル基、トリル基、o−キシリル基等の炭素数6〜30の芳香族炭化水素基;などが挙げられる。炭素数1〜30の炭化水素基としては、好ましくは炭素数1〜20のアルキル基であり、より好ましくは炭素数1〜10のアルキル基であり、さらに好ましくは炭素数1〜6のアルキル基であり、特に好ましくは炭素数1〜2のアルキル基であり、最も好ましくは炭素数1のアルキル基である。 As the hydrocarbon group having 1 to 30 carbon atoms in R 4 and R p , any appropriate hydrocarbon group having 1 to 30 carbon atoms can be adopted as long as the effect of the present invention is not impaired. Examples of such a hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a hexyl group; cyclopropyl. Cycloalkyl groups having 3 to 30 carbon atoms such as groups, cyclobutyl groups, cyclopentyl groups and cyclohexyl groups; aromatic hydrocarbon groups having 6 to 30 carbon atoms such as phenyl groups, benzyl groups, trill groups and o-xylyl groups; etc. Can be mentioned. The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms. It is particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably an alkyl group having 1 carbon atom.
R4、Rpにおける炭素数1〜30の炭化水素基は、置換基として水酸基、アルコキシ基、(ポリ)オキシアルキレン基、オキソ基含有基、ハロゲン原子、エポキシ基、およびカルボニル基からなる群より選択される少なくとも1種を有していてもよい。なお、これらの置換基を構成する炭素原子の数は、R2における「炭素数1〜30の炭化水素基」の炭素数には含まれないものとする。アルコキシ基としては、例えば、メトキシ基、エトキシ基等の炭素数1〜10のアルコキシ基が挙げられる。(ポリ)オキシアルキレン基としては、例えば、オキシエチレン基、オキシプロピレン基等の、アルキレン基の炭素数が1〜3であって、繰り返し数が1〜100の(ポリ)オキシアルキレン基が挙げられる。オキソ基含有基としては、例えば、スルホン酸基、リン酸基等のオキソ基含有基が挙げられる。ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子が挙げられる。エポキシ基としては、例えば、炭素数2〜8の環状エーテル含有基が挙げられる。 Hydrocarbon group R 4, carbon atoms in the R p 1 to 30 represents a hydroxyl group as a substituent, an alkoxy group, (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, epoxy group, and carbonyl group, It may have at least one selected. The number of carbon atoms constituting these substituents, shall not be included in the carbon number of the "hydrocarbon group having 1 to 30 carbon atoms" in R 2. Examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group. Examples of the (poly) oxyalkylene group include (poly) oxyalkylene groups having 1 to 3 carbon atoms and 1 to 100 repetitions of the alkylene group such as an oxyethylene group and an oxypropylene group. .. Examples of the oxo group-containing group include an oxo group-containing group such as a sulfonic acid group and a phosphoric acid group. Examples of the halogen atom include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the epoxy group include a cyclic ether-containing group having 2 to 8 carbon atoms.
R4、Rpとしては、好ましくは、水素原子、1価の金属原子、または第4級アンモニウム塩基であり、より好ましくは、水素原子または1価の金属原子である。 The R 4, R p, is preferably a hydrogen atom, a monovalent metal atom or a quaternary ammonium salt, more preferably a hydrogen atom or a monovalent metal atom.
一般式(1)で表される不飽和単量体(B)としては、本発明の効果を損なわない範囲で、任意の適切な一般式(1)で表される不飽和単量体(B)を採用し得る。このような一般式(1)で表される不飽和単量体(B)としては、例えば、(メタ)アクリル酸、クロトン酸、α−ヒドロキシアクリル酸等の不飽和モノカルボン酸およびこれらの塩;これらの不飽和モノカルボン酸とアルコールのエステル;マレイン酸、イタコン酸、シトラコン酸、フマル酸等の不飽和ジカルボン酸、これらの塩、およびこれらの無水物;これらの不飽和ジカルボン酸系単量体とアルコールとのハーフエステルおよびジエステル;メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、sec−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、トリデシル(メタ)アクリレート、n−ラウリル(メタ)アクリレート、ドデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等のアルキル(メタ)アクリレート;シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等のシクロアルキル(メタ)アクリレート;α−ヒドロキシメチルアクリレート、α−ヒドロキシエチルアクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート等の水酸基含有(メタ)アクリレート;エチレングリコールメトキシ(メタ)アクリレート、ジエチレングリコール(メタ)アクリレート、ジエチレングリコールメトキシ(メタ)アクリレート等の(ジ)エチレングリコール(メトキシ)(メタ)アクリレート、アルコキシポリエチレングリコールメタクリレート等のアルコキシポリアルキレングリコール(メタ)アクリレート;スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシエチルホスフェート等のオキソ基含有(メタ)アクリレート;トリフルオロエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート等のフルオロ基含有アルキル(メタ)アクリレート;グリシジル(メタ)アクリレート、α−メチルグリシジル(メタ)アクリレート、グリシジルアリルエーテル等のエポキシ基含有(メタ)アクリレート;アセトニル(メタ)アクリレート、ジアセトン(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレートアセチルアセテート、ブタンジオール−1,4−アクリレートアセチルアセテート、2−(アセトアセトキシ)エチル(メタ)アクリレート、(メタ)アクリロイルオキシアルキルプロペナール等のカルボニル基含有(メタ)アクリレート;などが挙げられる。 As the unsaturated monomer (B) represented by the general formula (1), any suitable unsaturated monomer (B) represented by the general formula (1) is used as long as the effects of the present invention are not impaired. ) Can be adopted. Examples of the unsaturated monomer (B) represented by the general formula (1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and α-hydroxyacrylic acid, and salts thereof. Acrylate of these unsaturated monocarboxylic acids and alcohols; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid, salts thereof, and anhydrides thereof; these unsaturated dicarboxylic acid-based single amounts. Body-alcohol half-esters and diesters; methyl (meth) acrylates, ethyl (meth) acrylates, n-propyl (meth) acrylates, isopropyl (meth) acrylates, n-butyl (meth) acrylates, isobutyl (meth) acrylates, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) Alkyl (meth) acrylates such as acrylates and stearyl (meth) acrylates; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylates and isobornyl (meth) acrylates; α-hydroxymethyl acrylates, α-hydroxyethyl acrylates, 2-hydroxy Hydroxyl group-containing (meth) acrylates such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; (Di) ethylene glycol (methoxy) (meth) acrylate such as ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate such as alkoxypolyethylene glycol methacrylate; Oxo group-containing (meth) acrylates such as sulfopropyl (meth) acrylates and (meth) acryloyloxyethyl phosphate; fluoros such as trifluoroethyl (meth) acrylates, tetrafluoropropyl (meth) acrylates and octafluoropentyl (meth) acrylates. Group-containing alkyl (meth) acrylate; glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, grease Epoxy group-containing (meth) acrylates such as sidylallyl ether; acetonyl (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, 2-( Examples thereof include acetoacetoxy) ethyl (meth) acrylate, carbonyl group-containing (meth) acrylate such as (meth) acryloyloxyalkylpropenal; and the like.
一般式(1)で表される不飽和単量体(B)としては、好ましくは、不飽和モノカルボン酸およびこれらの塩;不飽和モノカルボン酸と炭素数1〜22のアルコールとのエステル;不飽和ジカルボン酸、これらの塩、およびこれらの無水物;不飽和ジカルボン酸系単量体と炭素数1〜22のアルコールとのハーフエステルおよびジエステル;炭素数1〜30のアルキル(メタ)アクリレート;が好ましい。 The unsaturated monomer (B) represented by the general formula (1) is preferably an unsaturated monocarboxylic acid and a salt thereof; an ester of an unsaturated monocarboxylic acid and an alcohol having 1 to 22 carbon atoms; Unsaturated dicarboxylic acids, salts thereof, and anhydrides thereof; half-esters and diesters of unsaturated dicarboxylic acid-based monomers and alcohols having 1 to 22 carbon atoms; alkyl (meth) acrylates having 1 to 30 carbon atoms; Is preferable.
塩としては、本発明の効果を損なわない範囲で、任意の適切な塩を採用し得る。このような塩としては、たとえば、アルカリ金属塩、アルカリ土類金属塩、第4級アンモニウム塩などが挙げられ、好ましくはアルカリ金属塩である。 As the salt, any suitable salt may be adopted as long as the effects of the present invention are not impaired. Examples of such a salt include an alkali metal salt, an alkaline earth metal salt, a quaternary ammonium salt and the like, and an alkali metal salt is preferable.
不飽和単量体(B)が(ポリ)オキシアルキレン基を有する場合、好ましくは、炭素数3〜200の化合物であり、より好ましくは、炭素数7〜100の化合物であり、さらに好ましくは、炭素数7〜60の化合物である。また、不飽和単量体(B)が(ポリ)オキシアルキレン基を有する場合、好ましくは、オキシアルキレン基を構成するアルキレン基の炭素数が1〜5であり、オキシアルキレン基の繰り返し数が1〜100であり、(ポリ)オキシアルキレン基以外の構造における炭素数が3〜20である。アルキレン基の炭素数は、より好ましくは1〜4であり、さらに好ましくは1〜3である。オキシアルキレン基の繰り返し数は、より好ましくは1〜90であり、さらに好ましくは1〜80である。 When the unsaturated monomer (B) has a (poly) oxyalkylene group, it is preferably a compound having 3 to 200 carbon atoms, more preferably a compound having 7 to 100 carbon atoms, and even more preferably. It is a compound having 7 to 60 carbon atoms. When the unsaturated monomer (B) has a (poly) oxyalkylene group, the alkylene group constituting the oxyalkylene group preferably has 1 to 5 carbon atoms and the number of repetitions of the oxyalkylene group is 1. It is ~ 100 and has 3 to 20 carbon atoms in the structure other than the (poly) oxyalkylene group. The alkylene group has more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. The number of repetitions of the oxyalkylene group is more preferably 1 to 90, still more preferably 1 to 80.
不飽和単量体(B)が(ポリ)オキシアルキレン基を有しない場合、不飽和単量体(B)は、好ましくは、炭素数2〜50の化合物であり、より好ましくは、炭素数2〜40の化合物であり、さらに好ましくは、炭素数2〜30の化合物である。 When the unsaturated monomer (B) does not have a (poly) oxyalkylene group, the unsaturated monomer (B) is preferably a compound having 2 to 50 carbon atoms, and more preferably 2 carbon atoms. It is a compound of ~ 40, more preferably a compound having 2 to 30 carbon atoms.
不飽和単量体(B)は、好ましくは、一般式(2)で表される。 The unsaturated monomer (B) is preferably represented by the general formula (2).
一般式(2)中、R5は、水素原子またはメチル基を表し、R6は、水素原子、1価〜3価の金属原子、1価〜3価の金属原子を含む原子団、アンモニウム塩、置換基を有していてもよい(ポリ)オキシアルキレン基、または置換基として水酸基、アルコキシ基、(ポリ)オキシアルキレン基、オキソ基含有基、ハロゲン原子、エポキシ基、およびカルボニル基からなる群より選択される少なくとも1種を有していてもよい炭素数1〜30の炭化水素基を表す。 In the general formula (2), R 5 represents a hydrogen atom or a methyl group, and R 6 is an atomic group containing a hydrogen atom, a monovalent to trivalent metal atom, or a monovalent to trivalent metal atom, and an ammonium salt. , A group consisting of a (poly) oxyalkylene group which may have a substituent, or a hydroxyl group, an alkoxy group, a (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, an epoxy group, and a carbonyl group as the substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the above.
R6における1価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な1価の金属原子を採用し得る。このような1価の金属原子としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属原子が挙げられ、好ましくは、ナトリウム、カリウムである。 As the monovalent metal atom in R 6 , any appropriate monovalent metal atom may be adopted as long as the effect of the present invention is not impaired. Examples of such monovalent metal atoms include alkali metal atoms such as lithium, sodium and potassium, and sodium and potassium are preferable.
R6における2価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な2価の金属原子を採用し得る。このような2価の金属原子としては、例えば、カルシウム、マグネシウム等のアルカリ土類金属原子が挙げられる。 As the divalent metal atom in R 6 , any appropriate divalent metal atom can be adopted as long as the effect of the present invention is not impaired. Examples of such divalent metal atoms include alkaline earth metal atoms such as calcium and magnesium.
R6における3価の金属原子としては、本発明の効果を損なわない範囲で、任意の適切な3価の金属原子を採用し得る。このような3価の金属原子としては、例えば、アルミニウム、鉄などが挙げられる。 As the trivalent metal atom in R 6 , any appropriate trivalent metal atom may be adopted as long as the effect of the present invention is not impaired. Examples of such a trivalent metal atom include aluminum and iron.
R6における1価〜3価の金属原子を含む原子団としては、本発明の効果を損なわない範囲で、任意の適切な1価〜3価の金属原子を含む原子団を採用し得る。このような1価〜3価の金属原子を含む原子団としては、例えば、ジアンミン銀イオン、ビオレオ、テトラアンミン亜鉛(II)イオン、ヘキサアンミンニッケル(II)イオン、ヘキサアンミンクロム(III)イオン、ローゼオなどが挙げられる。 As the atomic group containing a monovalent to trivalent metal atom in R 6 , an atomic group containing any appropriate monovalent to trivalent metal atom may be adopted as long as the effect of the present invention is not impaired. Examples of the atomic group containing such monovalent to trivalent metal atoms include diammine silver ion, violeo, tetraammine zinc (II) ion, hexaammine nickel (II) ion, hexaammine chromium (III) ion, and roseo. And so on.
R6における置換基を有していてもよい(ポリ)オキシアルキレン基としては、本発明の効果を損なわない範囲で、任意の適切な置換基を有していてもよい(ポリ)オキシアルキレン基を採用し得る。このような置換基を有していてもよい(ポリ)オキシアルキレン基としては、例えば、下記一般式(A)で表される基が挙げられる。 The (poly) oxyalkylene group which may have a substituent in R 6 may have any appropriate substituent as long as the effect of the present invention is not impaired. Can be adopted. Examples of the (poly) oxyalkylene group which may have such a substituent include a group represented by the following general formula (A).
一般式(A)についての説明は、一般式(1)中のR4、Rpにおける置換基を有していてもよい(ポリ)オキシアルキレン基の説明中での記載をそのまま援用し得る。 Description of the general formula (A), it can be incorporated by reference to the description of the general formula (1) in R 4, which may have a substituent in R p (poly) in the description of the oxyalkylene group.
R6における炭素数1〜30の炭化水素基としては、本発明の効果を損なわない範囲で、任意の適切な炭素数1〜30の炭化水素基を採用し得る。このような炭素数1〜30の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基等の炭素数1〜30のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数3〜30のシクロアルキル基;フェニル基、ベンジル基、トリル基、o−キシリル基等の炭素数6〜30の芳香族炭化水素基;などが挙げられる。炭素数1〜30の炭化水素基としては、好ましくは炭素数1〜20のアルキル基であり、より好ましくは炭素数1〜10のアルキル基であり、さらに好ましくは炭素数1〜6のアルキル基であり、特に好ましくは炭素数1〜2のアルキル基であり、最も好ましくは炭素数1のアルキル基である。 As the hydrocarbon group having 1 to 30 carbon atoms in R 6 , any appropriate hydrocarbon group having 1 to 30 carbon atoms can be adopted as long as the effect of the present invention is not impaired. Examples of such a hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a hexyl group; cyclopropyl. Cycloalkyl groups having 3 to 30 carbon atoms such as groups, cyclobutyl groups, cyclopentyl groups and cyclohexyl groups; aromatic hydrocarbon groups having 6 to 30 carbon atoms such as phenyl groups, benzyl groups, trill groups and o-xylyl groups; etc. Can be mentioned. The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms. It is particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably an alkyl group having 1 carbon atom.
R6における炭素数1〜30の炭化水素基は、置換基として水酸基、アルコキシ基、(ポリ)オキシアルキレン基、オキソ基含有基、ハロゲン原子、エポキシ基、およびカルボニル基からなる群より選択される少なくとも1種を有していてもよい。なお、これらの置換基を構成する炭素原子の数は、R2における「炭素数1〜30の炭化水素基」の炭素数には含まれないものとする。アルコキシ基としては、例えば、メトキシ基、エトキシ基等の炭素数1〜10のアルコキシ基が挙げられる。(ポリ)オキシアルキレン基としては、例えば、オキシエチレン基、オキシプロピレン基等の、アルキレン基の炭素数が1〜3であって、繰り返し数が1〜100の(ポリ)オキシアルキレン基が挙げられる。オキソ基含有基としては、例えば、スルホン酸基、リン酸基等のオキソ基含有基が挙げられる。ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子が挙げられる。エポキシ基としては、例えば、炭素数2〜8の環状エーテル含有基が挙げられる。 The hydrocarbon group having 1 to 30 carbon atoms in R 6 is selected as a substituent from the group consisting of a hydroxyl group, an alkoxy group, a (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, an epoxy group, and a carbonyl group. It may have at least one kind. The number of carbon atoms constituting these substituents, shall not be included in the carbon number of the "hydrocarbon group having 1 to 30 carbon atoms" in R 2. Examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group. Examples of the (poly) oxyalkylene group include (poly) oxyalkylene groups having 1 to 3 carbon atoms and 1 to 100 repetitions of the alkylene group such as an oxyethylene group and an oxypropylene group. .. Examples of the oxo group-containing group include an oxo group-containing group such as a sulfonic acid group and a phosphoric acid group. Examples of the halogen atom include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the epoxy group include a cyclic ether-containing group having 2 to 8 carbon atoms.
R6としては、好ましくは、水素原子、1価〜3価の金属原子、1価〜3価の金属原子を含む原子団、アンモニウム塩、置換基を有していてもよい(ポリ)オキシアルキレン基、水酸基を有する炭素数1〜30の炭化水素基である。 R 6 preferably has a hydrogen atom, a monovalent to trivalent metal atom, an atomic group containing a monovalent to trivalent metal atom, an ammonium salt, and a substituent (poly) oxyalkylene. It is a hydrocarbon group having 1 to 30 carbon atoms having a group and a hydroxyl group.
一般式(2)で表される不飽和単量体(B)としては、好ましくは、(メタ)アクリル酸またはこれらの塩、上述の炭素数1〜30の炭化水素基をエステル部分に有する(メタ)アクリル酸エステルが挙げられる。 The unsaturated monomer (B) represented by the general formula (2) preferably has (meth) acrylic acid or a salt thereof, and the above-mentioned hydrocarbon group having 1 to 30 carbon atoms in the ester moiety (). Meta) Acrylic acid ester can be mentioned.
一般式(2)で表される不飽和単量体(B)由来の構造単位(b)は、好ましくは、(メタ)アクリル酸またはこれらの塩由来の構造単位、上述の炭素数1〜30の炭化水素基をエステル部分に有する(メタ)アクリル酸エステル由来の構造単位であり、より好ましくは、(メタ)アクリル酸またはこれらの塩由来の構造単位である。 The structural unit (b) derived from the unsaturated monomer (B) represented by the general formula (2) is preferably a structural unit derived from (meth) acrylic acid or a salt thereof, and has 1 to 30 carbon atoms as described above. It is a structural unit derived from (meth) acrylic acid ester having a hydrocarbon group of (meth) acrylic acid in the ester moiety, and more preferably, it is a structural unit derived from (meth) acrylic acid or a salt thereof.
ラクタム構造を有する不飽和単量体(A)は、ラクタム環とエチレン性不飽和炭化水素基とを有する単量体であり、好ましくは、一般式(3)で表される。 The unsaturated monomer (A) having a lactam structure is a monomer having a lactam ring and an ethylenically unsaturated hydrocarbon group, and is preferably represented by the general formula (3).
一般式(3)中、R8、R9、R10、R11は、同一または異なって、水素原子、炭素数1〜10のアルキル基、または上述した−COOR4で表される基を表す。xは、0〜5の整数を表す。yは、1〜3の整数を表す。 In the general formula (3), R 8 , R 9 , R 10 , and R 11 represent the same or different hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups represented by −COOR 4 described above. .. x represents an integer from 0 to 5. y represents an integer of 1-3.
R8、R9、R10、R11における炭素数1〜10のアルキル基の炭素数は、好ましくは1〜5であり、より好ましくは1〜3である。このようなアルキル基としては、例えば、メチル基、エチル基が挙げられ、好ましくはメチル基である。 The number of carbon atoms of the alkyl group having 1 to 10 carbon atoms in R 8 , R 9 , R 10 and R 11 is preferably 1 to 5, and more preferably 1 to 3. Examples of such an alkyl group include a methyl group and an ethyl group, and a methyl group is preferable.
R8、R9は、好ましくは水素原子である。 R 8 and R 9 are preferably hydrogen atoms.
R10は、好ましくは、水素原子または上述した−COOR4で表される基である。R10が上述した−COOR4で表される基である場合、−COOR4で表される基におけるR4は、好ましくは、水素原子または炭素数1〜8のアルキル基である。 R 10 is preferably a hydrogen atom or a group represented by -COOR 4 described above. If R 10 is a group represented by -COOR 4 described above, R 4 in the group represented by -COOR 4 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R11は、好ましくは、水素原子またはメチル基であり、より好ましくは水素原子である。 R 11 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
xは、好ましくは0〜4の整数であり、より好ましくは0〜3の整数であり、さらに好ましくは0である。 x is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably 0.
yは、好ましくは1または2であり、より好ましくは1である。 y is preferably 1 or 2, and more preferably 1.
一般式(3)で表される化合物としては、例えば、N−ビニルピロリドン、N−ビニル−5−メチルピロリドン、N−ビニルピペリドン、N−ビニルカプロラクタム、1−(2−プロペニル)−2−ピロリドン、一般式(4)で表される化合物が挙げられる。一般式(3)で表される化合物は、1種のみであってもよいし、2種以上であってもよい。 Examples of the compound represented by the general formula (3) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1- (2-propenyl) -2-pyrrolidone, and the like. Examples thereof include a compound represented by the general formula (4). The compound represented by the general formula (3) may be only one kind or two or more kinds.
一般式(4)中、R12は、水素原子または炭素数1〜8のアルキル基を表す。 In the general formula (4), R 12 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
一般式(3)で表される化合物としては、好ましくは、ピロリドン環を有する不飽和単量体であり、より好ましくは、N−ビニルピロリドンである。 The compound represented by the general formula (3) is preferably an unsaturated monomer having a pyrrolidone ring, and more preferably N-vinylpyrrolidone.
本発明の保湿剤用ポリマーは、構造単位(a)および構造単位(b)以外の、その他の単量体(E)由来の構造単位(e)を有していてもよい。 The polymer for a moisturizer of the present invention may have a structural unit (e) derived from another monomer (E) other than the structural unit (a) and the structural unit (b).
その他の単量体(E)としては、本発明の効果を損なわない範囲で、任意の適切なその他の単量体を採用し得る。このようなその他の単量体としては、例えば、アクリルアミドが挙げられる。 As the other monomer (E), any suitable other monomer may be adopted as long as the effect of the present invention is not impaired. Examples of such other monomers include acrylamide.
本発明の保湿剤用ポリマーは、構造単位(a)の割合が、全構造単位100質量%に対して、好ましくは30質量%〜99質量%であり、より好ましくは40質量%〜97質量%であり、さらに好ましくは45質量%〜95質量%であり、特に好ましくは50質量%〜90質量%である。 In the moisturizing agent polymer of the present invention, the ratio of the structural unit (a) is preferably 30% by mass to 99% by mass, more preferably 40% by mass to 97% by mass, based on 100% by mass of the total structural units. It is more preferably 45% by mass to 95% by mass, and particularly preferably 50% by mass to 90% by mass.
本発明の保湿剤用ポリマーは、構造単位(b)の割合が、全構造単位100質量%に対して、好ましくは1質量%〜70質量%であり、より好ましくは3質量%〜60質量%であり、さらに好ましくは5質量%〜50質量%であり、特に好ましくは10質量%〜50質量%である。 In the moisturizing agent polymer of the present invention, the ratio of the structural unit (b) is preferably 1% by mass to 70% by mass, more preferably 3% by mass to 60% by mass, based on 100% by mass of the total structural units. It is more preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 50% by mass.
本発明の保湿剤用ポリマーは、構造単位(e)の割合が、全構造単位100質量%に対して、好ましくは0質量%〜30質量%であり、より好ましくは0質量%〜20質量%であり、さらに好ましくは0質量%〜10質量%であり、特に好ましくは0質量%〜8質量%であり、最も好ましくは0質量%〜5質量%である。 In the moisturizing agent polymer of the present invention, the ratio of the structural unit (e) is preferably 0% by mass to 30% by mass, more preferably 0% by mass to 20% by mass, based on 100% by mass of the total structural units. It is more preferably 0% by mass to 10% by mass, particularly preferably 0% by mass to 8% by mass, and most preferably 0% by mass to 5% by mass.
本発明の保湿剤用ポリマーは、構造単位(b)の割合が、構造単位(a)100質量%に対して、好ましくは1質量%〜200質量%であり、より好ましくは5質量%〜100質量%であり、さらに好ましくは10質量%〜70質量%である。上記の割合が上記の範囲内にあれば、本発明の保湿剤用ポリマーの親水性および疎水性のバランスがより良好なものとなる。 In the moisturizer polymer of the present invention, the ratio of the structural unit (b) is preferably 1% by mass to 200% by mass, more preferably 5% by mass to 100% by mass, based on 100% by mass of the structural unit (a). It is by mass%, more preferably 10% by mass to 70% by mass. When the above ratio is within the above range, the balance between hydrophilicity and hydrophobicity of the polymer for moisturizer of the present invention becomes better.
本発明の保湿剤用ポリマーは、ポリマーの固形分25質量%水溶液の粘度が、好ましくは300mPa・s〜10000mPa・sであり、より好ましくは500mPa・s〜7000mPa・sである。上記粘度が上記の範囲内にあれば、本発明の保湿剤用ポリマーを化粧品に配合した際に、系全体の増粘が抑制され、配合量の制限が少なくなり得る。上記粘度は、B型粘度計により測定することができる。 The polymer for a moisturizer of the present invention has a viscosity of an aqueous solution having a solid content of 25% by mass, preferably 300 mPa · s to 10000 mPa · s, and more preferably 500 mPa · s to 7000 mPa · s. When the viscosity is within the above range, when the polymer for a moisturizer of the present invention is blended into cosmetics, the thickening of the entire system can be suppressed and the limitation of the blending amount can be reduced. The viscosity can be measured with a B-type viscometer.
本発明の保湿剤用ポリマーは、好ましくは、水溶性である。ここで、本発明の保湿剤用ポリマーが水溶性であるとは、25℃において、そのポリマー0.5gを100gの水に溶解した際に、不溶分が0.5重量%未満であることをいう。 The moisturizer polymer of the present invention is preferably water-soluble. Here, the fact that the polymer for a moisturizer of the present invention is water-soluble means that when 0.5 g of the polymer is dissolved in 100 g of water at 25 ° C., the insoluble content is less than 0.5% by weight. Say.
本発明の保湿剤用ポリマーの構造は、本発明の効果を損なわない範囲で、任意の適切な構造を採用し得る。このような構造としては、例えば、ランダム共重合体構造、グラフト構造、ブロック共重合体構造、グラジエント共重合体構造、星形構造、デンドリマー構造などが挙げられる。 As the structure of the polymer for a moisturizer of the present invention, any suitable structure can be adopted as long as the effect of the present invention is not impaired. Examples of such a structure include a random copolymer structure, a graft structure, a block copolymer structure, a gradient copolymer structure, a star-shaped structure, and a dendrimer structure.
≪保湿剤用ポリマーの製造方法≫
本発明の保湿剤用ポリマーの製造方法としては、本発明の効果を損なわない範囲で、任意の適切な製造方法を採用し得る。このような製造方法としては、代表的には、単量体成分を重合することにより製造することができ、単量体成分の具体例および好ましい例は、上述の通りである。
≪Manufacturing method of polymer for moisturizer≫
As a method for producing the polymer for a moisturizer of the present invention, any appropriate production method can be adopted as long as the effects of the present invention are not impaired. As such a production method, it can be typically produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component are as described above.
本発明の保湿剤用ポリマーの原料となる単量体成分におけるラクタム構造を有する不飽和単量体(A)の含有割合は、全単量体100質量%に対して、好ましくは30質量%〜99質量%であり、より好ましくは40質量%〜97質量%であり、さらに好ましくは45質量%〜95質量%であり、特に好ましくは50質量%〜90質量%である。 The content ratio of the unsaturated monomer (A) having a lactam structure in the monomer component which is the raw material of the polymer for a moisturizing agent of the present invention is preferably 30% by mass to 100% by mass with respect to 100% by mass of all the monomers. It is 99% by mass, more preferably 40% by mass to 97% by mass, further preferably 45% by mass to 95% by mass, and particularly preferably 50% by mass to 90% by mass.
本発明の保湿剤用ポリマーの原料となる単量体成分における一般式(1)で表される不飽和単量体(B)の含有割合は、全単量体100質量%に対して、好ましくは1質量%〜70質量%であり、より好ましくは3質量%〜60質量%であり、さらに好ましくは5質量%〜50質量%であり、特に好ましくは10質量%〜50質量%である。 The content ratio of the unsaturated monomer (B) represented by the general formula (1) in the monomer component which is the raw material of the polymer for a moisturizing agent of the present invention is preferably 100% by mass of all the monomers. Is 1% by mass to 70% by mass, more preferably 3% by mass to 60% by mass, further preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 50% by mass.
本発明の保湿剤用ポリマーの原料となる単量体成分におけるその他の単量体(E)の割合は、全単量体100質量%に対して、好ましくは0質量%〜30質量%であり、より好ましくは0質量%〜20質量%であり、さらに好ましくは0質量%〜10質量%であり、特に好ましくは0質量%〜8質量%であり、最も好ましくは0質量%〜5質量%である。 The ratio of the other monomer (E) in the monomer component which is the raw material of the polymer for the moisturizing agent of the present invention is preferably 0% by mass to 30% by mass with respect to 100% by mass of all the monomers. , More preferably 0% by mass to 20% by mass, further preferably 0% by mass to 10% by mass, particularly preferably 0% by mass to 8% by mass, and most preferably 0% by mass to 5% by mass. Is.
本発明の保湿剤用ポリマーの原料となる単量体成分における一般式(1)で表される不飽和単量体(B)の含有割合は、ラクタム構造を有する不飽和単量体(A)の合計100質量%に対して、好ましくは1質量%〜200質量%であり、より好ましくは5質量%〜100質量%であり、さらに好ましくは10質量%〜70質量%である。 The content ratio of the unsaturated monomer (B) represented by the general formula (1) in the monomer component which is the raw material of the polymer for a moisturizing agent of the present invention is the unsaturated monomer (A) having a lactam structure. It is preferably 1% by mass to 200% by mass, more preferably 5% by mass to 100% by mass, and further preferably 10% by mass to 70% by mass, based on 100% by mass of the total.
本発明の保湿剤用ポリマーの重合は、溶剤の不存在下で行ってもよいし、溶剤の存在下で行ってもよい。重合方法としては、通常用いられる方法、例えば、溶液重合法、懸濁重合法、逆相懸濁重合法、注型重合法、薄膜重合法、噴霧重合法が挙げられる。 The polymerization of the moisturizer polymer of the present invention may be carried out in the absence of a solvent or in the presence of a solvent. Examples of the polymerization method include commonly used methods such as a solution polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a casting polymerization method, a thin film polymerization method, and a spray polymerization method.
単量体成分の重合を開始する方法としては、例えば、重合開始剤を添加する方法、UVを照射する方法、熱を加える方法、光開始剤存在下に光を照射する方法が挙げられる。 Examples of the method for initiating the polymerization of the monomer component include a method of adding a polymerization initiator, a method of irradiating with UV, a method of applying heat, and a method of irradiating light in the presence of a photoinitiator.
本発明の保湿剤用ポリマーは、単量体成分を重合開始剤の存在下で重合する方法により製造することが好ましい。単量体成分を重合させる際には、重合方法に応じて重合開始剤を適宜用いることができる。重合開始剤としては、例えば、過酸化水素;過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩;ジメチル2,2’−アゾビス(2−メチルプロピオネート)、2,2’−アゾビス(イソブチロニトリル)、2,2’−アゾビス(2−メチルプロピオンアミジン)二塩酸塩、2,2’−アゾビス[N−(2−カルボキシエチル)−2−メチルプロピオンアミジン]水和物、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]二塩酸塩、2,2’−アゾビス(1−イミノ−1−ピロリジノ−2−メチルプロパン)二塩酸塩等のアゾ系化合物;過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ−t−ブチルパーオキサイド、クメンヒドロパーオキサイド等の有機過酸化物;アスコルビン酸と過酸化水素、スルホキシル酸ナトリウムとt−ブチルヒドロパーオキシド、過硫酸塩と金属塩等の、酸化剤と還元剤とを組み合わせてラジカルを発生させる酸化還元型開始剤;などが挙げられる。これらの重合開始剤のうち、残存単量体が減少する傾向にあることから、好ましくは、過酸化水素、過硫酸塩、アゾ系化合物から選ばれる少なくとも1種であり、より好ましくはアゾ系化合物である。重合開始剤は、1種のみであってもよいし、2種以上であってもよい。 The polymer for a moisturizer of the present invention is preferably produced by a method of polymerizing a monomer component in the presence of a polymerization initiator. When polymerizing the monomer component, a polymerization initiator can be appropriately used depending on the polymerization method. Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis. (Isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'- Azobisisobutyate (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and other azo compounds; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like Peroxide: An oxidation-reduction initiator that generates radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, sodium sulfoxylate and t-butyl hydroperoxide, and persulfate and metal salt; And so on. Of these polymerization initiators, since the residual monomer tends to decrease, it is preferably at least one selected from hydrogen peroxide, persulfate, and azo compound, and more preferably an azo compound. Is. The polymerization initiator may be only one kind or two or more kinds.
重合開始剤の使用量は、単量体成分の重合を開始できる量であれば、本発明の効果を損なわない範囲で、任意の適切な量を採用し得る。このような重合開始剤の使用量は、全単量体成分100質量部に対して、好ましくは0.01質量部〜30質量部であり、より好ましくは0.02質量部〜20質量部であり、さらに好ましくは0.05質量部〜10質量部である。 As the amount of the polymerization initiator used, any appropriate amount can be adopted as long as the polymerization of the monomer component can be started, as long as the effect of the present invention is not impaired. The amount of such a polymerization initiator used is preferably 0.01 parts by mass to 30 parts by mass, and more preferably 0.02 parts by mass to 20 parts by mass with respect to 100 parts by mass of all the monomer components. Yes, more preferably 0.05 parts by mass to 10 parts by mass.
重合の際には、必要に応じて連鎖移動剤を用いてもよい。連鎖移動剤としては、具体的には、例えば、メルカプトエタノール、チオグリコール酸、メルカプトプロピオン酸、n−ドデシルメルカプタン等の、チオール系連鎖移動剤;四塩化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等の、ハロゲン化物;イソプロピルアルコール、グリセリン等の、第2級アルコール;次亜リン酸、次亜リン酸ナトリウム等の次亜リン酸(塩)(これらの水和物を含む);亜リン酸、亜リン酸ナトリウム等の亜リン酸(塩);亜硫酸ナトリウム、亜硫酸カリウム等の亜硫酸(塩);亜硫酸水素ナトリウム、亜硫酸水素カリウム等の重亜硫酸(塩);亜ジチオン酸ナトリウム等の亜ジチオン酸(塩);ピロ亜硫酸カリウム等のピロ亜硫酸(塩);などが挙げられる。連鎖移動剤は、1種のみであってもよいし、2種以上であってもよい。 At the time of polymerization, a chain transfer agent may be used if necessary. Specific examples of the chain transfer agent include thiol-based chain transfer agents such as mercaptoethanol, thioglycolic acid, mercaptopropionic acid, and n-dodecyl mercaptan; carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane and the like. , Halogen; Secondary alcohols such as isopropyl alcohol and glycerin; Hypophosphorous acid (salts) such as hypophosphorous acid and sodium hypophosphate (including hydrates thereof); Phosphorous acid, Sub Phosphorous acid (salt) such as sodium phosphate; sulfite (salt) such as sodium sulfite and potassium sulfite; bisulfite (salt) such as sodium hydrogen sulfite and potassium hydrogen sulfite; sodium dithionite (salt) such as sodium dithionite ); Pyrophosphate (salt) such as potassium pyrosulfite; The chain transfer agent may be only one type or two or more types.
連鎖移動剤の使用量は、全単量体の使用量1モルに対して、好ましくは0g以上60g以下であり、より好ましくは0g以上50g以下である。 The amount of the chain transfer agent used is preferably 0 g or more and 60 g or less, and more preferably 0 g or more and 50 g or less, based on 1 mol of the total monomer used.
重合においては、反応促進等を目的として、重金属イオンを使用しても良い。重金属イオンとは、比重が4g/cm3以上の金属のイオンを意味する。重金属イオンを使用することで、重合開始剤の使用量を低減することが可能となる。重金属イオンは、イオンの形態として含まれるものであれば、任意の適切な重金属イオンを採用し得る。このような重金属イオンとしては、重金属化合物を溶解してなる溶液を用いると、取り扱い性に優れるため好適である。このような重金属化合物としては、例えば、モール塩(Fe(NH4)2(SO4)2・6H2O)、硫酸第一鉄・7水和物、塩化第一鉄、塩化第二鉄、塩化マンガンなどが挙げられる。 In the polymerization, heavy metal ions may be used for the purpose of promoting the reaction and the like. The heavy metal ion means a metal ion having a specific gravity of 4 g / cm 3 or more. By using heavy metal ions, it is possible to reduce the amount of the polymerization initiator used. As the heavy metal ion, any suitable heavy metal ion may be adopted as long as it is contained in the form of an ion. As such a heavy metal ion, it is preferable to use a solution obtained by dissolving a heavy metal compound because it is excellent in handleability. Such heavy metal compounds, for example, Mohr's salt (Fe (NH 4) 2 ( SO 4) 2 · 6H 2 O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride, Examples include manganese chloride.
重金属イオンの使用量は、重合反応液全量に対して、好ましくは0ppm以上100ppm以下であり、より好ましくは0ppm以上50ppm以下であり、特に好ましくは0ppm以上20ppm以下である。 The amount of heavy metal ions used is preferably 0 ppm or more and 100 ppm or less, more preferably 0 ppm or more and 50 ppm or less, and particularly preferably 0 ppm or more and 20 ppm or less, based on the total amount of the polymerization reaction solution.
重合を行う際において、単量体成分や重合開始剤等の反応容器への添加方法としては、反応容器に単量体成分の全てを仕込み、重合開始剤を反応容器内に添加することによって共重合を行う方法;反応容器に単量体成分の一部を仕込み、重合開始剤と残りの単量体成分を反応容器内に連続してあるいは段階的に(好ましくは連続して)添加することによって共重合を行う方法;反応容器に重合溶媒を仕込み、単量体成分と重合開始剤の全量を添加する方法;反応容器に重合溶媒を仕込み、重合開始剤と単量体成分を反応容器に逐次滴下する方法;単量体のうちの一(例えば、ラクタム構造を有する不飽和単量体)の一部を反応容器に仕込み、重合開始剤と残りの単量体成分を反応容器内に(好ましくは連続して)添加することによって共重合を行う方法;などが挙げられる。このような方法の中でも、得られるポリマーの分子量分布を狭く(シャープに)することができ得ることから、重合開始剤と単量体成分を反応容器に逐次滴下する方法が好ましい。 When performing polymerization, as a method of adding the monomer component, the polymerization initiator, etc. to the reaction vessel, all the monomer components are charged in the reaction vessel, and the polymerization initiator is added into the reaction vessel. Method of performing polymerization: A part of the monomer component is charged into the reaction vessel, and the polymerization initiator and the remaining monomer component are added continuously or stepwise (preferably continuously) into the reaction vessel. Method of copolymerizing with the above; a method of charging a polymerization solvent in a reaction vessel and adding the entire amount of the monomer component and the polymerization initiator; a method of charging the polymerization solvent in the reaction vessel and putting the polymerization initiator and the monomer component in the reaction vessel. Method of sequentially dropping; a part of one of the monomers (for example, an unsaturated monomer having a lactam structure) is charged into the reaction vessel, and the polymerization initiator and the remaining monomer component are placed in the reaction vessel (for example, A method of copolymerizing by addition (preferably in succession); etc. Among such methods, the method of sequentially dropping the polymerization initiator and the monomer component into the reaction vessel is preferable because the molecular weight distribution of the obtained polymer can be narrowed (sharpened).
重合は、回分式でも連続式でも行うことができる。また、重合の際、必要に応じて使用される溶媒としては、例えば、水;メチルアルコール、エチルアルコール、イソプロピルアルコール(2−プロパノール)、ブタノール、THF(テトラヒドロフラン)等のアルコール類;グリセリン;ポリエチレングリコール;ベンゼン、トルエン、キシレン、シクロヘキサン、n−ヘプタン等の芳香族または脂肪族炭化水素類;酢酸エチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジメチルホルムアミド等のアミド類;ジエチルエーテル、ジオキサン等のエーテル類;などが挙げられる。これらの中でも、単量体成分および得られるポリマーの溶解性の点から、好ましくは、水および炭素数1〜4の低級アルコールからなる群より選択される少なくとも1種であり、より好ましくは、水、エタノール、イソプロピルアルコールからなる群より選択される少なくとも1種である。最も好ましくは、水である。溶媒は、比較的安価なものであり、本発明の保湿剤用ポリマーの製造方法は、経済的にも優れる。溶媒は、1種のみであってもよいし、2種以上であってもよい。 The polymerization can be carried out in a batch system or a continuous system. The solvent used as needed during polymerization includes, for example, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), butanol, and THF (tetra); glycerin; polyethylene glycol. Aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; diethyl ether, dioxane, etc. Ethers; etc. Among these, at least one selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms is preferable from the viewpoint of the solubility of the monomer component and the obtained polymer, and more preferably water. , Ethanol, isopropyl alcohol, at least one selected from the group. Most preferably, it is water. The solvent is relatively inexpensive, and the method for producing a polymer for a moisturizer of the present invention is economically excellent. The solvent may be only one kind or two or more kinds.
本発明の保湿剤用ポリマーの製造方法においては、必要に応じて、任意の他の添加剤、例えば、pH調節剤、緩衝剤などを用いることができる。 In the method for producing a polymer for a moisturizer of the present invention, any other additive such as a pH adjuster and a buffer can be used, if necessary.
重合の際の温度としては、好ましくは20℃〜100℃であり、より好ましくは40℃〜100℃である。重合の際の温度が上記範囲内にあれば、残存単量体成分が少なくなる傾向にある。なお、重合の際の温度は、重合反応の進行中において、常に一定に保持する必要はなく、例えば、室温から重合を開始し、適当な昇温時間または昇温速度で設定温度まで昇温し、その後、設定温度を保持するようにしてもよいし、単量体成分や開始剤等の滴下方法に応じて、重合反応の進行中に経時的に重合温度を変動(昇温または降温)させてもよい。また、単量体成分を重合させる際には、単量体成分が均一に重合するようにするために、適宜、撹拌することが好ましい。 The temperature at the time of polymerization is preferably 20 ° C. to 100 ° C., more preferably 40 ° C. to 100 ° C. If the temperature at the time of polymerization is within the above range, the residual monomer component tends to decrease. It is not necessary to keep the temperature at the time of polymerization constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate temperature rise time or rate. After that, the set temperature may be maintained, or the polymerization temperature may be changed (increased or lowered) with time during the progress of the polymerization reaction depending on the method of dropping the monomer component or the initiator. You may. Further, when the monomer component is polymerized, it is preferable to stir appropriately so that the monomer component is polymerized uniformly.
重合時間は、重合反応の進行状況に応じて適宜設定すればよい。このような重合時間としては、好ましくは1時間〜10時間である。なお、「重合時間」とは単量体を添加している時間を表す。 The polymerization time may be appropriately set according to the progress of the polymerization reaction. The polymerization time is preferably 1 hour to 10 hours. The "polymerization time" represents the time during which the monomer is added.
重合の際の反応系内の圧力としては、常圧(大気圧)下、減圧下、加圧下のいずれであってもよい。反応系内の雰囲気としては、空気雰囲気でも不活性ガス雰囲気でもどちらでもよい。不活性ガスとしては、例えば、窒素、アルゴンなどが挙げられ、好ましくは窒素である。 The pressure in the reaction system during polymerization may be normal pressure (atmospheric pressure), reduced pressure, or pressurized pressure. The atmosphere in the reaction system may be either an air atmosphere or an inert gas atmosphere. Examples of the inert gas include nitrogen, argon and the like, and nitrogen is preferable.
重合の際の反応系内において、重合反応が終了した時点での水溶液中の固形分濃度(すなわち単量体の重合固形分濃度)は、好ましくは10質量%以上であり、より好ましくは20質量%〜80質量%である。重合反応終了時の固形分濃度がこのように高ければ、高濃度かつ一段で重合を行うことができる。そのため、従来の製造方法では場合によっては必要であった濃縮工程を省略することができるなど、効率よく本発明の保湿剤用ポリマーを得ることができる。それゆえ、その製造効率を大幅に上昇させたものとすることができ、その結果、本発明の保湿剤用ポリマーの生産性を大幅に向上し、製造コストの上昇も抑制することが可能となる。 In the reaction system at the time of polymerization, the solid content concentration in the aqueous solution (that is, the polymerized solid content concentration of the monomer) at the time when the polymerization reaction is completed is preferably 10% by mass or more, more preferably 20% by mass. % -80% by mass. If the solid content concentration at the end of the polymerization reaction is as high as this, the polymerization can be carried out at a high concentration and in one step. Therefore, the polymer for a moisturizer of the present invention can be efficiently obtained, for example, the concentration step which is necessary in some cases in the conventional production method can be omitted. Therefore, the production efficiency can be significantly increased, and as a result, the productivity of the moisturizer polymer of the present invention can be significantly improved, and the increase in production cost can be suppressed. ..
本発明の保湿剤用ポリマーの製造方法は、全ての使用原料の添加が終了した以後に、単量体の重合率を上げること等を目的として熟成工程を設けても良い。熟成時間は、好ましくは1分間〜240分間であり、より好ましくは1分間〜180分間であり、さらに好ましくは1分間〜120分間である。熟成時間が1分間未満の場合には、熟成不十分につき単量体成分が残ることがあり、残存単量体に起因する毒性や臭気などが問題となる。 In the method for producing a polymer for a moisturizer of the present invention, an aging step may be provided for the purpose of increasing the polymerization rate of the monomer after the addition of all the raw materials used is completed. The aging time is preferably 1 minute to 240 minutes, more preferably 1 minute to 180 minutes, and even more preferably 1 minute to 120 minutes. If the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, and toxicity and odor caused by the residual monomer become a problem.
熟成工程における好ましい重合体溶液の温度は、上記重合温度と同様の範囲である。したがって、熟成工程における重合体溶液の温度も一定温度(好ましくは上記滴下が終了した時点での温度)で保持してもよいし、熟成中に経時的に温度を変化させてもよい。 The preferred temperature of the polymer solution in the aging step is in the same range as the above-mentioned polymerization temperature. Therefore, the temperature of the polymer solution in the aging step may be maintained at a constant temperature (preferably the temperature at the time when the dropping is completed), or the temperature may be changed over time during the aging.
本発明の保湿剤用ポリマーの製造方法は、得られたポリマーについて乾燥する工程(乾燥工程)を含んでもよい。 The method for producing a polymer for a moisturizer of the present invention may include a step (drying step) of drying the obtained polymer.
乾燥工程における乾燥温度としては、好ましくは80℃〜250℃である。乾燥工程における乾燥時間としては、好ましくは30分〜3時間である。 The drying temperature in the drying step is preferably 80 ° C. to 250 ° C. The drying time in the drying step is preferably 30 minutes to 3 hours.
乾燥工程は、乾燥工程の乾燥時間全体の50%以上の時間を80℃〜250℃の乾燥温度で行われることが好ましい。乾燥温度および乾燥時間が上記範囲内にあることにより、ポリマーの諸物性がより向上する傾向にある。乾燥工程は、より好ましくは、実質的に全ての乾燥工程を通して80℃〜250℃の乾燥温度で行われる。 The drying step is preferably carried out at a drying temperature of 80 ° C. to 250 ° C. for 50% or more of the total drying time of the drying step. When the drying temperature and the drying time are within the above ranges, the physical properties of the polymer tend to be further improved. The drying step is more preferably carried out at a drying temperature of 80 ° C. to 250 ° C. throughout substantially all the drying steps.
乾燥温度は熱媒温度で規定するが、マイクロ波等熱媒温度で規定できない場合は材料温度で規定する。 The drying temperature is specified by the heat medium temperature, but if it cannot be specified by the heat medium temperature such as microwaves, it is specified by the material temperature.
乾燥方法としては、例えば、熱風乾燥、無風乾燥、減圧乾燥、赤外線乾燥、マイクロ波乾燥などが挙げられる。これらの乾燥方法の中でも、熱風乾燥を用いることがより好ましい。熱風乾燥を用いる場合の乾燥風量は、好ましくは0.01m/sec〜10m/secであり、より好ましくは0.1m/sec〜5m/secである。 Examples of the drying method include hot air drying, windless drying, vacuum drying, infrared drying, microwave drying and the like. Among these drying methods, it is more preferable to use hot air drying. When hot air drying is used, the dry air volume is preferably 0.01 m / sec to 10 m / sec, and more preferably 0.1 m / sec to 5 m / sec.
乾燥温度の範囲は、より好ましくは110℃〜220℃であり、さらに好ましくは120℃〜200℃である。また、乾燥は、一定温度で乾燥してもよく、温度を変化させて乾燥してもよい。 The drying temperature range is more preferably 110 ° C. to 220 ° C., and even more preferably 120 ° C. to 200 ° C. Further, the drying may be performed at a constant temperature or may be performed by changing the temperature.
本発明の保湿剤用ポリマーの製造方法において、ポリマーの乾燥を行う場合、乾燥後のポリマーについて、粉砕および/または分級することが好ましい。より好ましくは、粉砕および分級の両方を行う。 In the method for producing a polymer for a moisturizer of the present invention, when the polymer is dried, it is preferable that the dried polymer is pulverized and / or classified. More preferably, both grinding and classification are performed.
粉砕する方法としては、例えば、ロールミルのようなロール式粉砕機、ハンマーミルのようなハンマー式粉砕機、衝撃式粉砕機、カッターミル、ターボグラインダー、ボールミル、フラッシュミル、ジェットミルなどを用いて粉砕する方法が挙げられる。このような粉砕する方法の中でも、粒度分布を制御するために、ロールミルを用いて粉砕する方法が好ましい。粒度分布を制御するために、連続して2回以上粉砕することがより好ましく、連続して3回以上粉砕することがさらに好ましい。また、2回以上粉砕する場合には、それぞれの粉砕機は同じであってもよいし、異なっていてもよい。異なる種類の粉砕機を組み合わせて使うことも可能である。 As a crushing method, for example, a roll crusher such as a roll mill, a hammer crusher such as a hammer mill, an impact crusher, a cutter mill, a turbo grinder, a ball mill, a flash mill, a jet mill, or the like is used for crushing. There is a way to do it. Among such pulverization methods, a method of pulverizing using a roll mill is preferable in order to control the particle size distribution. In order to control the particle size distribution, it is more preferable to pulverize twice or more continuously, and it is further preferable to pulverize three times or more continuously. Further, when crushing twice or more, each crusher may be the same or different. It is also possible to use different types of crushers in combination.
粉砕した紛体は、分級することができる。分級には、特定の目開きの篩を使用することができる。篩で分級するために用いる分級機としては、例えば、振動篩(アンバランスウェイト駆動式、共振式、振動モータ式、電磁式、円型振動式等)、面内運動篩(水平運動式、水平円−直線運動式、3次元円運動式等)、可動網式篩、強制攪拌式篩、網面振動式篩、風力篩、音波篩などが挙げられ、好ましくは、振動篩、面内運動篩である。 The crushed powder can be classified. A sieve with a specific opening can be used for classification. Examples of the classifier used for classifying with a sieve include a vibrating sieve (unbalanced weight drive type, resonance type, vibration motor type, electromagnetic type, circular vibration type, etc.) and an in-plane motion sieve (horizontal motion type, horizontal). Circular-linear motion type, three-dimensional circular motion type, etc.), movable net type sieve, forced stirring type sieve, net surface vibration type sieve, wind force sieve, sonic sieve, etc. are mentioned, and vibration sieve, in-plane motion sieve, etc. are preferable. Is.
≪保湿剤用ポリマーの用途≫
本発明の保湿剤用ポリマーは、保湿剤に用い得る。すなわち、本発明の保湿剤は、本発明の保湿剤用ポリマーを含む。
≪Use of polymer for moisturizer≫
The polymer for a moisturizer of the present invention can be used as a moisturizer. That is, the moisturizer of the present invention contains the polymer for the moisturizer of the present invention.
本発明の保湿剤中の保湿剤用ポリマーの含有割合は、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。このような保湿剤用ポリマーの含有割合としては、保湿剤100質量%に対して、好ましくは1質量%〜100質量%であり、より好ましくは2質量%〜100質量%であり、さらに好ましくは3質量%〜100質量%であり、特に好ましくは4質量%〜100質量%であり、最も好ましくは5質量%〜100質量%である。 As the content ratio of the moisturizer polymer in the moisturizer of the present invention, any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired. The content ratio of such a polymer for a moisturizing agent is preferably 1% by mass to 100% by mass, more preferably 2% by mass to 100% by mass, still more preferably, with respect to 100% by mass of the moisturizing agent. It is 3% by mass to 100% by mass, particularly preferably 4% by mass to 100% by mass, and most preferably 5% by mass to 100% by mass.
本発明の保湿剤中には、本発明の効果を損なわない範囲で、任意の適切な本発明の保湿剤用ポリマー以外の他の成分が含まれていてもよい。このような他の成分としては、例えば、水、油性基剤、保湿剤(本発明の保湿剤を除く)、感触向上剤、界面活性剤、高分子、増粘剤、ゲル化剤、溶剤、噴射剤、酸化防止剤、還元剤、酸化剤、防腐剤、抗菌剤、キレート剤、pH調整剤、酸、アルカリ、粉体類、無機塩、紫外線吸収剤、美白剤、ビタミン類およびその誘導体類、消炎剤、抗炎症剤、育毛用薬剤、血行促進剤、刺激剤、ホルモン類、抗しわ剤、抗老化剤、ひきしめ剤、冷感剤、温感剤、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤、植物・動物・微生物エキス、鎮痒剤、角質剥離・溶解剤、制汗剤、清涼剤、収れん剤、酵素、核酸、香料、色素、着色剤、染料、顔料などが挙げられる。このような他の成分は、1種のみであってもよいし、2種以上であってもよい。 The moisturizer of the present invention may contain any other component other than the appropriate appropriate polymer for the moisturizer of the present invention as long as the effects of the present invention are not impaired. Such other components include, for example, water, oily bases, moisturizers (excluding the moisturizers of the present invention), feel improvers, surfactants, polymers, thickeners, gelling agents, solvents, etc. Propellants, antioxidants, reducing agents, oxidizing agents, preservatives, antibacterial agents, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts, UV absorbers, whitening agents, vitamins and their derivatives , Anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cold sensation agents, warming agents, wound healing promoters, irritation palliatives, Painkillers, cell activators, plant / animal / microbial extracts, pruritus agents, keratin exfoliating / dissolving agents, antiperspirants, refreshing agents, astringents, enzymes, nucleic acids, fragrances, pigments, coloring agents, dyes, pigments, etc. Be done. Such other components may be only one kind or two or more kinds.
本発明の保湿剤中に含まれ得る他の成分としては、好ましくは、保湿剤(本発明の保湿剤を除く)、感触向上剤である。 Other components that can be contained in the moisturizer of the present invention are preferably a moisturizer (excluding the moisturizer of the present invention) and a feel improver.
保湿剤(本発明の保湿剤を除く)および感触向上剤としては、例えば、グリセリン、1,3−ブチレングリコール、プロピレングリコール、3−メチル−1,3−ブタンジオール、1,3−プロパンジオール、2−メチル−1,3−プロパンジオール、トリメチロールプロパン、ペンタエリスリトール、ヘキシレングリコール、ジグリセリン、ポリグリセリン、ジエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、エチレングリコール・プロピレングリコール共重合体等のポリオール類およびその重合体;ジエチレングリコールモノエチルエーテル(エトキシジグリコール)、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジブチルエーテル等のグリコールアルキルエーテル類;ソルビトール、キシリトール、エリスリトール、マンニトール、マルチトール等の糖アルコール類;グルコース、フルクトース、ガラクトース、マンノース、トレオース、キシロース、アラビノース、フコース、リボース、デオキシリボース、マルトース、トレハロース、ラクトース、ラフィノース、グルコン酸、グルクロン酸、シクロデキストリン類(α−、β−、γ−シクロデキストリン、および、マルトシル化、ヒドロキシアルキル化等の修飾シクロデキストリン)、β−グルカン、キチン、キトサン、ヘパリンおよび誘導体、ペクチン、アラビノガラクタン、デキストリン、デキストラン、グリコーゲン、エチルグルコシド、メタクリル酸グルコシルエチル重合物若しくは共重合物等の糖類およびその誘導体類;ヒアルロン酸、ヒアルロン酸ナトリウム;コンドロイチン硫酸ナトリウム;ムコイチン硫酸、カロニン硫酸、ケラト硫酸、デルマタン硫酸;シロキクラゲ抽出物、シロキクラゲ多糖体;フコイダン;チューベロース多糖体、天然由来多糖体;クエン酸、酒石酸、乳酸等の有機酸およびその塩;尿素;2−ピロリドン−5−カルボン酸およびそのナトリウム等の塩;ベタイン(トリメチルグリシン)、プロリン、ヒドロキシプロリン、アルギニン、リジン、セリン、グリシン、アラニン、フェニルアラニン、チロシン、β−アラニン、スレオニン、グルタミン酸、グルタミン、アスパラギン、アスパラギン酸、システイン、シスチン、メチオニン、ロイシン、イソロイシン、バリン、トリプトファン、ヒスチジン、タウリン等のアミノ酸類およびその塩;コラーゲン、魚由来コラーゲン、アテロコラーゲン、ゼラチン、エラスチン、コラーゲン分解ペプチド、加水分解コラーゲン、塩化ヒドロキシプロピルアンモニウム加水分解コラーゲン、エラスチン分解ペプチド、ケラチン分解ペプチド、加水分解ケラチン、コンキオリン分解ペプチド、加水分解コンキオリン、シルク蛋白分解ペプチド、加水分解シルク、ラウロイル加水分解シルクナトリウム、大豆蛋白分解ペプチド、小麦蛋白分解ペプチド、加水分解小麦蛋白、カゼイン分解ペプチド、アシル化ペプチド等の蛋白ペプチド類およびその誘導体;パルミトイルオリゴペプチド、パルミトイルペンタペプチド、パルミトイルテトラペプチド等のアシル化ペプチド類;シリル化ペプチド類;乳酸菌培養液、酵母抽出液、卵殻膜タンパク、牛顎下腺ムチン、ヒポタウリン、ゴマリグナン配糖体、グルタチオン、アルブミン、乳清;塩化コリン、ホスホリルコリン;胎盤抽出液、エアラスチン、コラーゲン、アロエ抽出物、ハマメリス水、ヘチマ水、カモミラエキス、カンゾウエキス、コンフリーエキス、シルクエキス、イザヨイバラエキス、セイヨウノコギリソウエキス、ユーカリエキス、メリロートエキス等の動物・植物抽出成分、天然型セラミド(タイプ1、2、3、4、5、6)、ヒドロキシセラミド、疑似セラミド、スフィンゴ糖脂質、セラミドおよび糖セラミド含有エキス等のセラミド類;などが挙げられる。これらの中でも、保湿剤(本発明の保湿剤を除く)および感触向上剤としては、好ましくは、グリセリン、1,3−ブチレングリコール、プロピレングリコール、3−メチル−1,3−ブタンジオール、1,3−プロパンジオール、2−メチル−1,3−プロパンジオール、トリメチロールプロパン、ペンタエリスリトール、ヘキシレングリコール、ジグリセリン、ポリグリセリン、ジエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、エチレングリコール・プロピレングリコール共重合体等のポリオール類およびその重合体;ヒアルロン酸、ヒアルロン酸ナトリウム;が挙げられ、より好ましくは、グリセリン、ヒアルロン酸が挙げられる。 Moisturizers (excluding the moisturizer of the present invention) and feel improvers include, for example, glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, and the like. 2-Methyl-1,3-propanediol, trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer, etc. Polyols and their polymers; Glycolalkyl ethers such as diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether; sorbitol, xylitol, erythritol, mannitol, maltitol, etc. Sugar alcohols; glucose, fructose, galactose, mannose, treose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, cyclodextrins (α-, β-, γ) -Cyclodextrin and modified cyclodextrins such as maltosylated and hydroxyalkylated), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabinogalactan, dextrin, dextran, glycogen, ethyl glucoside, glucosyl ethyl methacrylate Sugars such as polymers or copolymers and their derivatives; hyaluronic acid, sodium hyaluronate; sodium chondroitin sulfate; mucoitin sulfate, caronine sulfate, keratosulfate, dermatan sulfate; white jellyfish extract, white jellyfish polysaccharide; fucoidan; tuberose polysaccharide , Naturally-derived polysaccharides; organic acids such as citric acid, tartrate, lactic acid and salts thereof; urea; salts such as 2-pyrrolidone-5-carboxylic acid and sodium thereof; betaine (trimethylglycine), proline, hydroxyproline, arginine, Lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamate, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, valine, tryptophan, histidine, Amino acids such as taurine and salts thereof; collagen, fish-derived collagen, atelocollagen, gelatin, elastin, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin-degrading peptide, keratin-degrading peptide, hydrolyzed keratin, conchiolin Degrading peptides, hydrolyzed conchiolin, silk proteolytic peptides, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean proteolytic peptides, wheat proteolytic peptides, hydrolyzed wheat proteins, casein degrading peptides, acylated peptides and other protein peptides and Derivatives; acylated peptides such as palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide; silylated peptides; lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular gland mutin, hypotaurine, sesame lignan glycoside , Glutathion, albumin, lactate; choline chloride, phosphorylcholine; placenta extract, aerastin, collagen, aloe extract, hamamelis water, hechima water, chamomile extract, kanzo extract, comfrey extract, silk extract, izayoi rose extract, ceramide extract , Eucalyptus extract, melilot extract and other animal / plant extracts, natural ceramides (types 1, 2, 3, 4, 5, 6), hydroxyceramides, pseudo-ceramides, spingoglycolipids, ceramides and sugar ceramide-containing extracts, etc. Ceramides; etc. Among these, as the moisturizing agent (excluding the moisturizing agent of the present invention) and the feel improving agent, glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1, 3-Propylenediol, 2-Methyl-1,3-Propylenediol, Trimethylolpropane, Pentaerythritol, Hexylene glycol, Diglycerin, Polyglycerin, Diethylene glycol, Polyethylene glycol, Dipropylene glycol, Polypropylene glycol, Ethylene glycol / Propylene glycol Polyethylenes such as copolymers and polymers thereof; hyaluronic acid, sodium hyaluronate; are mentioned, and more preferably, glycerin and hyaluronic acid are mentioned.
ヒアルロン酸としては、代表的には、低分子ヒアルロン酸、高分子ヒアルロン酸が挙げられる。 Typical examples of hyaluronic acid include low molecular weight hyaluronic acid and high molecular weight hyaluronic acid.
本発明の保湿剤は、本発明の効果を損なわない範囲で、任意の適切な方法によって製造し得る。 The moisturizer of the present invention can be produced by any suitable method as long as the effects of the present invention are not impaired.
本発明の保湿剤用ポリマーは、皮膚化粧料、皮膚外用剤、または頭髪化粧料に用い得る。すなわち、本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料は、本発明の保湿剤用ポリマーを含む。 The moisturizer polymer of the present invention can be used for skin cosmetics, external preparations for skin, or hair cosmetics. That is, the skin cosmetics, external preparations for skin, or hair cosmetics of the present invention include the polymer for moisturizers of the present invention.
皮膚化粧料としては、本発明の効果を損なわない範囲で、任意の適切な皮膚化粧料に採用し得る。このような皮膚化粧料としては、例えば、基礎化粧料;白粉・打粉類、ファンデーション、下地乳液、チークカラー、アイライナー、アイシャドウ、マスカラ、口紅、リップグロス、眉墨、アイブロー、ネイルエナメル、エナメルリムーバー、ネイルトリートメント等のメイクアップ化粧料;クレンジングクリーム、洗顔フォーム、液状洗顔料等の洗浄用化粧料;日焼け止め化粧料等の化粧料(医薬部外品を含む);浴用剤等の浴用化粧料;歯磨き、マウスウォッシュ等の口腔内化粧料;香水、パフューム、パルファム、オードパルファム、オードトワレ、オーデコロン、練香水、芳香パウダー、香水石鹸、ボディローション、バスオイル等の芳香化粧料;ボディシャンプー等のボディ洗浄料、デオドラントローション、デオドラントパウダー、デオドラントスプレー、デオドラントスティック、脱色剤、脱毛・除毛剤、浴用剤;虫よけスプレー等のインセクトリペラー等のボディ化粧料;などが挙げられる。 As the skin cosmetics, any suitable skin cosmetics can be used as long as the effects of the present invention are not impaired. Examples of such skin cosmetics include basic cosmetics; white powder / dusting powder, foundation, foundation emulsion, teak color, eyeliner, eyeshadow, mascara, lipstick, lip gloss, eyebrow, eyebrow, nail enamel, and enamel remover. , Makeup cosmetics such as nail treatment; Cleaning cosmetics such as cleansing cream, face wash foam, liquid wash pigment; Cosmetics such as sunscreen cosmetics (including non-medicinal products); Bath cosmetics such as bathing agents Oral cosmetics such as toothpaste and mouthwash; Fragrant cosmetics such as perfume, perfume, parfum, eau de parfum, eau de toilette, eau de colon, kneaded perfume, aromatic powder, perfume soap, body lotion, bath oil; body cleaning such as body shampoo Agents, deodorant lotions, deodorant powders, deodorant sprays, deodorant sticks, decolorants, hair removers / hair removers, bathing agents; body cosmetics such as insect repellents such as insect repellents; etc.
基礎化粧料としては、より具体的には、例えば、柔軟化粧水、収れん化粧水、洗浄用化粧水、多層式化粧水等の化粧水;エモリエントローション、モイスチャーローション、ミルキィーローション、ナリシングローション、ナリシングミルク、スキンモイスチャー、モイスチャーエマルション、マッサージローション、クレンジングローション、プロテクトエマルション、サンプロテクト、サンプロテクター、UVケアミルク、サンスクリーン、メーキャップローション、角質スムーザー、エルボーローション、ハンドローション、ボディローション等の乳液;エモリエントクリーム、栄養クリーム、ナリシングクリーム、バニシングクリーム、モイスチャークリーム、ナイトクリーム、マッサージクリーム、クレンジングクリーム、メーキャップクリーム、ベースクリーム、プレメーキャップクリーム、サンスクリーンクリーム、サンタンクリーム、除毛クリーム、デオドラントクリーム、シェービングクリーム、角質軟化クリーム等のクリーム;モイスチャージェル等のジェル;保湿エッセンス、美白エッセンス、紫外線防止エッセンス等のエッセンス;リポソーム美容液、リポソーム化粧水等のリポソーム化粧品類;ピールオフパック、粉末パック、ウォッシングパック、オイルパック、クレンジングマスク等のパック・マスク類;クレンジングフォーム、クレンジングクリーム、クレンジングミルク、クレンジングローション、クレンジングジェル、クレンジングオイル、クレンジングマスク、洗粉、洗顔パウダー等の洗顔料;化粧石鹸、透明石鹸、薬用石鹸、液状石鹸、ひげそり石鹸、合成化粧石鹸等の石鹸;などが挙げられる。 More specifically, as basic cosmetics, for example, soft lotions, astringent lotions, cleansing lots, multi-layer lotions and the like; emollient lotions, moisture lotions, milky lotions, nourishing lotions, nari Emollients such as Thing Milk, Skin Moisture, Moisture Emulsion, Massage Lotion, Cleansing Lotion, Protect Emulsion, Sun Protect, Sun Protector, UV Care Milk, Sun Screen, Makeup Lotion, Horny Smoother, Elbow Lotion, Hand Lotion, Body Lotion; Cream, Nourishing Cream, Nourishing Cream, Vanishing Cream, Moisture Cream, Night Cream, Massage Cream, Cleansing Cream, Makeup Cream, Base Cream, Premakeup Cream, Sunscreen Cream, Suntan Cream, Hair Removal Cream, Deodorant Cream, Shaving Cream , Cream such as keratin softening cream; Gel such as moisturizing gel; Essence such as moisturizing essence, whitening essence, UV protection essence; Lipstick cosmetics such as liposome beauty liquid, liposome lotion; peel-off pack, powder pack, washing pack, oil Packs and masks such as packs and cleansing masks; cleansing foams, cleansing creams, cleansing milks, cleansing lotions, cleansing gels, cleansing oils, cleansing masks, powders, facial cleansing powders and other washing pigments; cosmetic soaps, clear soaps, medicated soaps, etc. Examples thereof include liquid soaps, shaving soaps, and synthetic cosmetic soaps.
皮膚外用剤としては、本発明の効果を損なわない範囲で、任意の適切な皮膚外用剤に採用し得る。このような皮膚外用剤としては、例えば、リニメント剤、ローション剤、軟膏剤等の外用医薬品などが挙げられる。 As the external preparation for skin, any suitable external preparation for skin can be used as long as the effects of the present invention are not impaired. Examples of such external preparations for skin include external preparations such as liniment agents, lotions, and ointments.
頭髪化粧料としては、本発明の効果を損なわない範囲で、任意の適切な頭髪化粧料に採用し得る。このような頭髪化粧料としては、例えば、オイルシャンプー、クリームシャンプー、コンディショニングシャンプー、ふけ用シャンプー、ヘアカラー用シャンプー、リンス一体型シャンプー等のシャンプー;リンス、トリートメント、ヘアパック、カラーローション、枝毛コート、パーマネントウェーブ用剤、ストレートパーマ剤、酸化染毛剤、ヘアブリーチ、ヘアカラープレトリートメント、ヘアカラーアフタートリートメント、パーマプレトリートメント、パーマアフタートリートメント、ヘアマニキュア、ヘアトニック、育毛剤、ワックス、スプレー、ジェル、ミストなどが挙げられる。なお、頭髪化粧料として、整髪剤は除かれる。 As the hair cosmetic, it can be adopted as any suitable hair cosmetic as long as the effect of the present invention is not impaired. Such hair cosmetics include, for example, shampoos such as oil shampoo, cream shampoo, conditioning shampoo, indulgence shampoo, hair coloring shampoo, and rinse-integrated shampoo; rinse, treatment, hair pack, color lotion, and split hair coat. , Permanent wave agent, straight perm agent, oxidative hair dye, hair bleach, hair color pretreatment, hair color after treatment, perm pretreatment, perm after treatment, hair manicure, hair tonic, hair restorer, wax, spray, gel , Mist, etc. Hair styling products are excluded as hair cosmetics.
本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料中の保湿剤用ポリマーの含有割合は、本発明の効果を損なわない範囲で、任意の適切な保湿剤用ポリマーの含有割合を採用し得る。このような保湿剤用ポリマーの含有割合としては、保湿剤100質量%に対して、好ましくは0.01質量%〜10質量%であり、より好ましくは0.05質量%〜5質量%である。 For the content ratio of the moisturizer polymer in the skin cosmetics, skin external preparations, or hair cosmetics of the present invention, any appropriate moisturizer polymer content ratio is adopted as long as the effects of the present invention are not impaired. obtain. The content ratio of such a polymer for a moisturizer is preferably 0.01% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass with respect to 100% by mass of the moisturizer. ..
本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料には、本発明の効果を損なわない範囲で、任意の適切な添加成分が含まれていてもよい。このような添加成分としては、例えば、水、油性基剤、保湿剤(本発明の保湿剤を除く)、感触向上剤、界面活性剤、高分子、増粘剤、ゲル化剤、溶剤、噴射剤、酸化防止剤、還元剤、酸化剤、防腐剤、抗菌剤、キレート剤、pH調整剤、酸、アルカリ、粉体類、無機塩、紫外線吸収剤、美白剤、ビタミン類およびその誘導体類、消炎剤、抗炎症剤、育毛用薬剤、血行促進剤、刺激剤、ホルモン類、抗しわ剤、抗老化剤、ひきしめ剤、冷感剤、温感剤、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤、植物・動物・微生物エキス、鎮痒剤、角質剥離・溶解剤、制汗剤、清涼剤、収れん剤、酵素、核酸、香料、色素、着色剤、染料、顔料などが挙げられる。このような添加成分は、1種のみであってもよいし、2種以上であってもよい。 The skin cosmetics, external preparations for skin, or hair cosmetics of the present invention may contain any suitable additive component as long as the effects of the present invention are not impaired. Examples of such additive components include water, oil-based bases, moisturizers (excluding moisturizers of the present invention), feel improvers, surfactants, polymers, thickeners, gelling agents, solvents, and jets. Agents, antioxidants, reducing agents, oxidizing agents, preservatives, antibacterial agents, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts, UV absorbers, whitening agents, vitamins and their derivatives, Anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cold sensation agents, warming agents, wound healing promoters, irritation relievers, analgesia Agents, cell activators, plant / animal / microbial extracts, antipruritic agents, keratin exfoliating / dissolving agents, anti-inflammatory agents, refreshing agents, astringents, enzymes, nucleic acids, fragrances, pigments, colorants, dyes, pigments, etc. .. Such an additive component may be only one kind or two or more kinds.
水としては、例えば、常水、精製水の他、硬水、軟水、天然水、海洋深層水、電解アルカリイオン水、電解酸性イオン水、イオン水、クラスター水などが挙げられる。 Examples of water include normal water, purified water, hard water, soft water, natural water, deep ocean water, electrolytic alkaline ionized water, electrolytically acidic ionized water, ionized water, cluster water and the like.
油性基剤としては、例えば、セタノール、ミリスチルアルコール、オレイルアルコール、ラウリルアルコール、セトステアリルアルコール、ステアリルアルコール、アラキルアルコール、ベヘニルアルコール、ホホバアルコール、キミルアルコール、セラキルアルコール、バチルアルコール、ヘキシルデカノール、イソステアリルアルコール、2−オクチルドデカノール、ダイマージオール等の高級アルコール類;ベンジルアルコール等のアラルキルアルコールおよび誘導体;ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ベヘン酸、ウンデシレン酸、12−ヒドロキシステアリン酸、パルミトオレイン酸、オレイン酸、リノール酸、リノレイン酸、エルカ酸、ドコサヘキサエン酸、エイコサペンタエン酸、イソヘキサデカン酸、アンテイソヘンイコサン酸、長鎖分岐脂肪酸、ダイマー酸、水素添加ダイマー酸等の高級脂肪酸類およびそのアルミニウム塩、カルシウム塩、マグネシウム塩、亜鉛塩、カリウム塩等の金属石けん類、およびアミド等の含窒素誘導体類;流動パラフィン(ミネラルオイル)、重質流動イソパラフィン、軽質流動イソパラフィン、α−オレフィンオリゴマー、ポリイソブテン、水添ポリイソブテン、ポリブテン、スクワラン、オリーブ由来スクワラン、スクワレン、ワセリン、固型パラフィン等の炭化素類;キャンデリラワックス、カルナウバワックス、ライスワックス、木ろう、みつろう、モンタンワックス、オゾケライト、セレシン、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタム、フィッシャートロプシュワックス、ポリエチレンワックス、エチレン・プロピレンコポリマー等のワックス類;ヤシ油、パーム油、パーム核油、サフラワー油、オリーブ油、ヒマシ油、アボカド油、ゴマ油、茶油、月見草油、小麦胚芽油、マカデミアナッツ油、ヘーゼルナッツ油、ククイナッツ油、ローズヒップ油、メドウフォーム油、パーシック油、ティートリー油、ハッカ油、トウモロコシ油、ナタネ油、ヒマワリ油、小麦胚芽油、アマニ油、綿実油、大豆油、落花生油、コメヌカ油、カカオ脂、シア脂、水素添加ヤシ油、水素添加ヒマシ油、ホホバ油、水素添加ホホバ油等の植物油脂類;牛脂、乳脂、馬脂、卵黄油、ミンク油、タートル油等の動物性油脂類;鯨ロウ、ラノリン、オレンジラッフィー油等の動物性ロウ類;液状ラノリン、還元ラノリン、吸着精製ラノリン、酢酸ラノリン、酢酸液状ラノリン、ヒドロキシラノリン、ポリオキシエチレンラノリン、ラノリン脂肪酸、硬質ラノリン脂肪酸、ラノリンアルコール、酢酸ラノリンアルコール、酢酸(セチル・ラノリル)エステル等のラノリン類;レシチン、ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルセリン、ホスファチジルグリセロール、ホスファチジルイノシトール、スフィンゴミエリン等のスフィンゴリン脂質、ホスファチジン酸、リゾレシチン等のリン脂質類;水素添加大豆リン脂質、部分水素添加大豆リン脂質、水素添加卵黄リン脂質、部分水素添加卵黄リン脂質等のリン脂質誘導体類;コレステロール、ジヒドロコレステロール、ラノステロール、ジヒドロラノステロール、フィトステロール、コール酸等のステロール類;サポゲニン類;サポニン類;酢酸コレステリル、ノナン酸コレステリル、ステアリン酸コレステリル、イソステアリン酸コレステリル、オレイン酸コレステリル、N−ラウロイル−L−グルタミン酸ジ(コレステリル/ベヘニル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(コレステリル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(フィトステリル/ベヘニル/オクチルドデシル)、N−ラウロイル−L−グルタミン酸ジ(フィトステリル/オクチルドデシル)、N−ラウロイルサルコシンイソプロピル等のアシルサルコシンアルキルエステル、12−ヒドロキシステアリン酸コレステリル、マカデミアナッツ油脂肪酸コレステリル、マカデミアナッツ油脂肪酸フィトステリル、イソステアリン酸フィトステリル、軟質ラノリン脂肪酸コレステリル、硬質ラノリン脂肪酸コレステリル、長鎖分岐脂肪酸コレステリル、長鎖α−ヒドロキシ脂肪酸コレステリル等のステロールエステル類;リン脂質・コレステロール複合体、リン脂質・フィトステロール複合体等の脂質複合体;ミリスチン酸オクチルドデシル、ミリスチン酸ヘキシルデシル、イソステアリン酸オクチルドデシル、パリミチン酸セチル、パルミチン酸オクチルドデシル、オクタン酸セチル、オクタン酸ヘキシルデシル、イソノナン酸イソトリデシル、イソノナン酸イソノニル、イソノナン酸オクチル、イソノナン酸イソトリデシル、ネオペンタン酸イソデシル、ネオペンタン酸イソトリデシル、ネオペンタン酸イソステアリル、ネオデカン酸オクチルドデシル、オレイン酸オレイル、オレイン酸オクチルドデシル、リシノレイン酸オクチルドデシル、ラノリン脂肪酸オクチルドデシル、ジメチルオクタン酸ヘキシルデシル、エルカ酸オクチルドデシル、イソステアリン酸硬化ヒマシ油、オレイン酸エチル、アボカド油脂肪酸エチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン酸オクチル、イソステアリン酸イソプロピル、ラノリン脂肪酸イソプロピル、セバチン酸ジエチル、セバチン酸ジイソプロピル、セバチン酸ジオクチル、アジピン酸ジイソプロピル、セバチン酸ジブチルオクチル、アジピン酸ジイソブチル、コハク酸ジオクチル、クエン酸トリエチル等のモノアルコールカルボン酸エステル類;乳酸セチル、リンゴ酸ジイソステアリル、モノイソステアリン酸水添ヒマシ油等のオキシ酸エステル類;トリオクタン酸グリセリル、トリオレイン酸グリセリル、トリイソステアリン酸グリセリル、ジイソステアリン酸グリセリル、トリ(カプリル酸/カプリン酸)グリセリル、トリ(カプリル酸/カプリン酸/ミリスチン酸/ステアリン酸)グリセリル、水添ロジントリグリセリド(水素添加エステルガム)、ロジントリグリセリド(エステルガム)、ベヘン酸エイコサン二酸グリセリル、トリオクタン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、ジオクタン酸ネオペンチルグリコール、ジカプリン酸ネオペンチルグリコール、ジオクタン酸2−ブチル−2−エチル−1,3−プロパンジオール、ジオレイン酸プロピレングリコール、テトラオクタン酸ペンタエリスリチル、水素添加ロジンペンタエリスリチル、トリエチルヘキサン酸ジトリメチロールプロパン、(イソステアリン酸/セバシン酸)ジトリメチロールプロパン、トリエチルヘキサン酸ペンタエリスリチル、(ヒドロキシステアリン酸/ステアリン酸/ロジン酸)ジペンタエリスリチル、ジイソステアリン酸ジグリセリル、テトライソステアリン酸ポリグリセリル、ノナイソステアリン酸ポリグリセリル−10、デカ(エルカ酸/イソステアリン酸/リシノレイン酸)ポリグリセリル−8、(ヘキシルデカン酸/セバシン酸)ジグリセリルオリゴエステル、ジステアリン酸グリコール(ジステアリン酸エチレングリコール)等の多価アルコール脂肪酸エステル類;ダイマージリノール酸ジイソプロピル、ダイマージリノール酸ジイソステアリル、ダイマージリノール酸ジ(イソステアリル/フィトステリル)、ダイマージリノール酸(フィトステリル/ベヘニル)、ダイマージリノール酸(フィトステリル/イソステアリル/セチル/ステアリル/ベヘニル)、ダイマージリノール酸ダイマージリノレイル、ジイソステアリン酸ダイマージリノレイル、ダイマージリノレイル水添ロジン縮合物、ダイマージリノール酸硬化ヒマシ油、ヒドロキシアルキルダイマージリノレイルエーテル等のダイマー酸若しくはダイマージオールの誘導体;ヤシ油脂肪酸モノエタノールアミド(コカミドMEA)、ヤシ油脂肪酸ジエタノールアミド(コカミドDEA)、ラウリン酸モノエタノールアミド(ラウラミドMEA)、ラウリン酸ジエタノールアミド(ラウラミドDEA)、ラウリン酸モノイソプロパノールアミド(ラウラミドMIPA)、パルミチン酸モノエタノールアミド(パルタミドMEA)、パルミチン酸ジエタノールアミド(パルタミドDEA)、ヤシ油脂肪酸メチルエタノールアミド(コカミドメチルMEA)等の脂肪酸アルカノールアミド類;ジメチコン(ジメチルポリシロキサン)、高重合ジメチコン(高重合ジメチルポリシロキサン)、シクロメチコン(環状ジメチルシロキサン、デカメチルシクロペンタシロキサン)、フェニルトリメチコン、ジフェニルジメチコン、フェニルジメチコン、ステアロキシプロピルジメチルアミン、(アミノエチルアミノプロピルメチコン/ジメチコン)コポリマー、ジメチコノール、ジメチコノールクロスポリマー、シリコーン樹脂、シリコーンゴム、アミノプロピルジメチコンおよびアモジメチコン等のアミノ変性シリコーン、カチオン変性シリコーン、ジメチコンコポリオール等のポリエーテル変性シリコーン、ポリグリセリン変性シリコーン、糖変性シリコーン、カルボン酸変性シリコーン、リン酸変性シリコーン、硫酸変性シリコーン、アルキル変性シリコーン、脂肪酸変性シリコーン、アルキルエーテル変性シリコーン、アミノ酸変性シリコーン、ペプチド変性シリコーン、フッ素変性シリコーン、カチオン変性およびポリエーテル変性シリコーン、アミノ変性およびポリエーテル変性シリコーン、アルキル変性およびポリエーテル変性シリコーン、ポリシロキサン・オキシアルキレン共重合体等のシリコーン類;パーフルオロデカン、パーフルオロオクタン、パーフルオロポリエーテル等のフッ素系油剤類;などが挙げられる。 Examples of the oily base include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, setostearyl alcohol, stearyl alcohol, araquil alcohol, behenyl alcohol, jojoba alcohol, chimil alcohol, seraquil alcohol, batyl alcohol, hexyldecanol, and isostearyl. Higher alcohols such as alcohols, 2-octyldodecanols and dimerdiols; aralkyl alcohols and derivatives such as benzyl alcohol; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylene acid, 12-hydroxystearic Acids, palmitooleic acid, oleic acid, linoleic acid, linoleic acid, erucic acid, docosahexaenoic acid, eikosapentaenoic acid, isohexadecanoic acid, anteisohenicosanoic acid, long-chain branched fatty acids, dimer acid, hydrogenated dimer acid, etc. Higher fatty acids and metal soaps such as aluminum salts, calcium salts, magnesium salts, zinc salts and potassium salts, and nitrogen-containing derivatives such as amides; liquid paraffin (mineral oil), heavy liquid isoparaffin, light liquid isoparaffin , Α-Olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalane, vaseline, solid paraffin and other carbides; candelilla wax, carnauba wax, rice wax, wood wax, honey wax, montane Waxes such as wax, ozokelite, selecin, paraffin wax, microcrystallin wax, petrolatum, fishertroph wax, polyethylene wax, ethylene / propylene copolymer; palm oil, palm oil, palm kernel oil, safflower oil, olive oil, castor oil, Avocado oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rose hip oil, meadowfoam oil, persic oil, tea tree oil, peppermint oil, corn oil, rapeseed oil, sunflower oil, Vegetable fats and oils such as wheat germ oil, flaxseed oil, cotton seed oil, soybean oil, peanut oil, rice bran oil, cacao butter, shea butter, hydrogenated palm oil, hydrogenated castor oil, jojoba oil, hydrogenated jojoba oil; beef fat, milk fat , Horse fat, egg yolk oil, mink oil, turtle oil and other animal fats and oils; whale wax, lanolin, orange raffy oil and other animal waxes; liquid lanolin, reduced lanoli Lanolins such as adsorption-purified lanolin, lanolin acetate, liquid acetate lanolin, hydroxylanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, lanolin alcohol acetate, acetic acid (cetyl lanolyl) ester; lecithin, phosphatidylcholine , Phospholipid ethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingomyelin and other sphingophospholipids, phosphatidic acid, lysolecithin and other phospholipids; hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogenated egg yolk phospholipids Phospholipid derivatives such as partially hydrogenated egg yolk phospholipids; sterols such as cholesterol, dihydrocholesterol, lanosterol, dihydrolanosterol, phytosterol, cholic acid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, Cholesteryl isostearate, cholesteryl oleate, di-lauroyl-L-glutamate (cholesteryl / behenyl / octyldodecyl), di-lauroyl-L-glutamate (cholesteryl / octyldodecyl), di-lauroyl-L-glutamate (phytosteryl) / Behenyl / octyldodecyl), di-lauroyl-L-glutamate (phytosteryl / octyldodecyl), acylsarcosine alkyl esters such as N-lauroyl sarcosin isopropyl, cholesteryl 12-hydroxystearate, macadamia nut oil fatty acid cholesteryl, macadamia nut oil fatty acid phytosteryl , Phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long-chain branched fatty acid cholesteryl, long-chain α-hydroxy fatty acid cholesteryl and other sterol esters; phospholipid / cholesterol complex, phospholipid / phytosterol complex and other lipids Complex; octyldodecyl myristate, hexyldecyl myristate, octyldodecyl isostearate, cetyl parimitinate, octyldodecyl palmitate, cetyl octanate, hexyldecyl octanoate, isotolideyl isononanoate, isononyl isononanoate, octyl isononanoate Isotridecyl, Isodecyl neopentate, Isotridecyl neopentate, Isostearyl neopentate, Octane neodecanoate Tildodecyl, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanolin, hexyldecyl dimethyloctanoate, octyldodecyl erucate, hardened isostearic acid castor oil, ethyl oleate, avocado oil fatty acid ethyl, isopropyl myristate , Isopropyl palmitate, octyl palmitate, isopropyl isostearate, lanolin fatty acid isopropyl, diethyl sebatate, diisopropyl sebatate, dioctyl sebatate, diisopropyl adipate, dibutyl octyl sebatate, diisobutyl adipate, dioctyl succinate, triethyl citrate, etc. Monoalcoholic carboxylic acid esters; oxyacid esters such as cetyl lactate, diisostearyl malate, hydrogenated monoisostearate castor oil; glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate, tri (Caprylic acid / capric acid) glyceryl, tri (caprylic acid / capric acid / myristic acid / stearic acid) glyceryl, hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl benate eicosanate, Trimethylol propane trioctanoate, trimethyl propane triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, 2-butyl-2-ethyl-1,3-propanediol dioctanoate, propylene glycol dioleate, tetraoctanoic acid Pentaerythrityl, hydrogenated rosin pentaerythricyl, ditrimethylolpropane triethylhexanoic acid, ditrimethylolpropane (isostearic acid / sebacic acid), pentaerythricyl triethylhexanoate, (hydroxystearic acid / stearic acid / logonic acid) dipentaerythrityl, diisostearate Diglyceryl acid, polyglyceryl tetraisostearate, polyglyceryl nonaisostearate-10, deca (erucic acid / isostearic acid / ricinoleic acid) polyglyceryl-8, (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene distearate) Polyhydric alcohol fatty acid esters such as glycol); diisopropyl dimerginolate, diisosteari dimersinolate Le, Dimer dilinolate (isostearyl / phytosteryl), Dimergilinoleic acid (phytosteryl / behenyl), Dimerjilinolic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), Dimerdilinoleyl, Dimeric acid or derivatives of dimer diols such as diisostearate dimer dilinoleil, dimer dilinoleil hydrogenated rosin condensate, dimer dilinol acid-cured castor oil, hydroxyalkyl dimer dilinoleil ether; palm oil fatty acid monoethanolamide (cocamide) MEA), palm oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramide MIPA), palmitate monoethanolamide (partamide MEA) ), Palmitate diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamidomethyl MEA) and other fatty acid alkanolamides; dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic) Dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone, diphenyldimethicone, phenyldimethicone, stearoxypropyldimethylamine, (aminoethylaminopropylmethicone / dimethicone) copolymer, dimethiconol, dimethiconol crosspolymer, silicone resin, silicone rubber, amino Amino-modified silicones such as propyldimethicone and amodimethicone, cationic-modified silicones, polyether-modified silicones such as dimethicone copolyol, polyglycerin-modified silicones, sugar-modified silicones, carboxylic acid-modified silicones, phosphate-modified silicones, sulfate-modified silicones, alkyl-modified Silicone, fatty acid-modified silicone, alkyl ether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cationic-modified and polyether-modified silicone, amino-modified and polyether-modified silicone, alkyl-modified and polyether-modified silicone, polysiloxane. Silicones such as oxyalkylene copolymer; fluorine-based oils such as perfluorodecane, perfluorooctane, and perfluoropolyether ; And so on.
保湿剤(本発明の保湿剤を除く)および感触向上剤としては、前述の本発明の保湿剤に含まれ得る保湿剤(本発明の保湿剤を除く)、感触向上剤の説明をそのまま援用し得る。 As the moisturizer (excluding the moisturizer of the present invention) and the feel improver, the description of the moisturizer (excluding the moisturizer of the present invention) and the feel improver that can be contained in the above-mentioned moisturizer of the present invention is used as it is. obtain.
界面活性剤としては、例えば、陰イオン性界面活性剤、非イオン界面活性剤、陽イオン性界面活性剤、両性界面活性剤、高分子界面活性剤等などが挙げられる。界面活性剤のHLBとしては、代表的には、1程度の低いものから20程度の高いものまで使用でき、HLB低いものと高いものを組み合わせてもよい。 Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants and the like. As the HLB of the surfactant, typically, a low HLB of about 1 to a high HLB of about 20 can be used, and a combination of a low HLB and a high HLB may be used.
陰イオン性界面活性剤としては、例えば、ラウリン酸カリウム、ミリスチン酸カリウム等の脂肪酸塩;ラウリル硫酸ナトリウム、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩;ラウレス硫酸ナトリウム、ラウレス硫酸トリエタノールアミン等のポリオキシエチレンアルキル硫酸塩;ココイルメチルタウリンナトリウム、ココイルメチルタウリンカリウム、ラウロイルメチルタウリンナトリウム、ミリストイルメチルタウリンナトリウム、ラウロイルメチルアラニンナトリウム、ラウロイルサルコシンナトリウム、ラウロイルサルコシントリエタノールアミン、ラウロイルグルタミン酸メチルアラニンナトリウム等のアシルN−メチルアミノ酸塩;ココイルグルタミン酸ナトリウム、ココイルグルタミン酸トリエタノールアミン、ラウロイルグルタミン酸ナトリウム、ミリストイルグルタミン酸ナトリウム、ステアロイルグルタミン酸ナトリウム、パルミトイルアスパラギン酸ジトリエタノールアミン、ココイルアラニントリエタノールアミン等のアシルアミノ酸塩;ラウレス酢酸ナトリウム等のポリオキシエチレンアルキルエーテル酢酸塩;ラウロイルモノエタノールアミドコハク酸ナトリウム等のコハク酸エステル塩;脂肪酸アルカノールアミドエーテルカルボン酸塩;アシル乳酸塩;ポリオキシエチレン脂肪アミン硫酸塩;脂肪酸アルカノールアミド硫酸塩;硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等の脂肪酸グリセリド硫酸塩;アルキルベンゼンポリオキシエチレン硫酸塩;α−オレフィンスルホン酸ナトリウム等のオレフィンスルホン酸塩;スルホコハク酸ラウリル2ナトリウム、スルホコハク酸ジオクチルナトリウム等のアルキルスルホコハク酸塩;スルホコハク酸ラウレス2ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等のアルキルエーテルスルホコハク酸塩;テトラデシルベンゼンスルホン酸ナトリウム、テトラデシルベンゼンスルホン酸トリエタノールアミン等のアルキルベンゼンスルホン酸塩;アルキルナフタレンスルホン酸塩;アルカンスルホン酸塩;α−スルホ脂肪酸メチルエステル塩;アシルイセチオン酸塩;アルキルグリシジルエーテルスルホン酸塩;アルキルスルホ酢酸塩;ラウレスリン酸ナトリウム、ジラウレスリン酸ナトリウム、トリラウレスリン酸ナトリウム、モノオレスリン酸ナトリウム等のアルキルエーテルリン酸エステル塩;ラウリルリン酸カリウム等のアルキルリン酸エステル塩;カゼインナトリウム;アルキルアリールエーテルリン酸塩;脂肪酸アミドエーテルリン酸塩;ホスファチジルグリセロール、ホスファチジルイノシトール、ホスファチジン酸等のリン脂質類;カルボン酸変性シリコーン、リン酸変性シリコーン、硫酸変性シリコーン等のシリコーン系陰イオン性界面活性剤;などが挙げられる。 Examples of the anionic surfactant include fatty acid salts such as potassium laurate and potassium myristate; alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate and ammonium lauryl sulfate; sodium laureth sulfate and triethanol laureth sulfate. Polyoxyethylene alkyl sulfates such as amines; sodium cocoyl methyl taurine, potassium cocoyl methyl taurine, sodium lauroyl methyl taurine, sodium myristyl methyl taurine, sodium lauroyl methyl alanine, sodium lauroyl sarcosin, sodium lauroyl sarcosin triethanolamine, sodium methyl alanine lauroyl glutamate. Acyl N-methyl amino acid salts such as: Sodium cocoyl glutamate, Triethanolamine cocoyl glutamate, Sodium lauroyl glutamate, Sodium myristyl glutamate, Sodium stearoyl glutamate, Ditriethanolamine palmitoyl aspartate, Acylamino acids such as cocoylalanine triethanolamine; Laures Polyoxyethylene alkyl ether acetate such as sodium acetate; succinate ester salt such as sodium lauroyl monoethanolamide succinate; fatty acid alkanolamide ether carboxylate; acyl lactate; polyoxyethylene fatty amine sulfate; fatty acid alkanolamide sulfate Salt; Hardened palm oil fatty acid Fatty acid glyceride sulfate such as sodium glycerin sulfate; Alkylbenzene polyoxyethylene sulfate; Olefin sulfonate such as α-olefin sulfonate; Alkyl sulfosuccinate such as lauryl lauryl sulfosuccinate, sodium dioctyl sulfosuccinate Acids; Alkyl ether sulfosuccinates such as laureth sulfosuccinate disodium, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium, lauryl polypropylene glycol sodium sulfosuccinate; sodium tetradecylbenzene sulfonate, triethanolamine tetradecylbenzene sulfonate Alkylbenzene sulfonates such as: Alkylnaphthalene sulfonates; Alcan sulfonates; α-sulfo fatty acid methyl ester salts; Acylisethionates; Alkylglycidyl ether sulfonates; Alkyl sulfoacetates; Sodium laures phosphate, dilaures phosphate Alkyl ether phosphates such as sodium, sodium trilaures phosphate, sodium monoolesphosphate; alkyl phosphates such as potassium lauryl phosphate; sodium caseinate; alkylaryl ether phosphates; fatty acid amide ether phosphates; phosphatidyl Phosphate lipids such as glycerol, phosphatidylinositol, and phosphatidic acid; silicone-based anionic surfactants such as carboxylic acid-modified silicone, phosphoric acid-modified silicone, and sulfate-modified silicone; and the like.
非イオン界面活性剤としては、例えば、ラウレス(ポリオキシエチレンラウリルエーテル)類、セテス(ポリオキシエチレンセチルエーテル)類、ステアレス(ポリオキシエチレンステアリルエーテル)類、ベヘネス類(ポリオキシエチレンベヘニルエーテル)、イソステアレス(ポリオキシエチレンイソステアリルエーテル)類、オクチルドデセス(ポリオキシエチレンオクチルドデシルエーテル)類等の種々のポリオキシエチレン付加数のポリオキシエチレンアルキルエーテル類;ポリオキシエチレンアルキルフェニルエーテル;ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油モノイソステアレート、ポリオキシエチレン硬化ヒマシ油トリイソステアレート、ポリオキシエチレン硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、ポリオキシエチレン硬化ヒマシ油マレイン酸等のヒマシ油および硬化ヒマシ油誘導体;ポリオキシエチレンフィトステロール;ポリオキシエチレンコレステロール;ポリオキシエチレンコレスタノール;ポリオキシエチレンラノリン;ポリオキシエチレン還元ラノリン;ポリオキシエチレン・ポリオキシプロピレンセチルエーテル、ポリオキシエチレン・ポリオキシプロピレン2−デシルテトラデシルエーテル、ポリオキシエチレン・ポリオキシプロピレンモノブチルエーテル、ポリオキシエチレン・ポリオキシプロピレン水添ラノリン、ポリオキシエチレン・ポリオキシプロピレングリセリンエーテル等のポリオキシエチレン・ポリオキシプロピレンアルキルエーテル;ポリオキシエチレン・ポリオキシプロピレングリコール;PPG−9ジグリセリル等の(ポリ)グリセリンポリオキシプロピレングリコール;ステアリン酸グリセリル、イソステアリン酸グリセリル、パルミチン酸グリセリル、ミリスチン酸グリセリル、オレイン酸グリセリル、ヤシ油脂肪酸グリセリル、モノ綿実油脂肪酸グリセリン、モノエルカ酸グリセリン、セスキオレイン酸グリセリン、α,α’−オレイン酸ピログルタミン酸グリセリン、モノステアリン酸グリセリンリンゴ酸等のグリセリン脂肪酸部分エステル類;ステアリン酸ポリグリセリル−2、同3、同4、同5、同6、同8、同10、ジステアリン酸ポリグリセリル−6、同10、トリステアリン酸ポリグリセリル−2、デカステアリン酸ポリグリセリル−10、イソステアリン酸ポリグリセリル−2、同3、同4、同5、同6、同8、同10、ジイソステアリン酸ポリグリセリル−2(ジイソステアリン酸ジグリセリル)、同3、同10、トリイソステアリン酸ポリグリセリル−2、テトライソステアリン酸ポリグリセリル−2、デカイソステアリン酸ポリグリセリル−10、オレイン酸ポリグリセリル−2、同3、同4、同5、同6、同8、同10、ジオレイン酸ポリグリセリル−6、トリオレイン酸ポリグリセリル−2、デカオレイン酸ポリグリセリル−10等のポリグリセリン脂肪酸エステル;モノステアリン酸エチレングリコール等のエチレングリコールモノ脂肪酸エステル;モノステアリン酸プロピレングリコール等のプロピレングリコールモノ脂肪酸エステル;ペンタエリスリトール部分脂肪酸エステル;ソルビトール部分脂肪酸エステル;マルチトール部分脂肪酸エステル;マルチトールエーテル;ソルビタンモノオレエート、ソルビタンモノイソステアレート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ−2−エチルヘキシル酸ジグリセロールソルビタン、テトラ−2−エチルヘキシル酸ジグリセロールソルビタン等のソルビタン脂肪酸エステル;ショ糖脂肪酸エステル、メチルグルコシド脂肪酸エステル、ウンデシレン酸トレハロース等の糖誘導体部分エステル;カプリリルグルコシド等のアルキルグルコシド;アルキルポリグリコシド;ラノリンアルコール;還元ラノリン;ポリオキシエチレンジステアレート、ポリチレングリコールジイソステアレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンジオレエート等のポリオキシエチレン脂肪酸モノおよびジエステル;ポリオキシエチレン・プロピレングリコール脂肪酸エステル;ポリオキシエチレングリセリンモノステアレート、ポリオキシエチレングリセリンモノイソステアレート、ポリオキシエチレングリセリントリイソステアレート等のポリオキシエチレンモノオレエート等のポリオキシエチレングリセリン脂肪酸エステル;ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレート、ポリオキシエチレンソルビタンテトラオレエート等のポリオキシエチレンソルビタン脂肪酸エステル;ポリオキシエチレンソルビトールモノラウレート、ポリオキシエチレンソルビトールモノオレエート、ポリオキシエチレンソルビトールペンタオレエート、ポリオキシエチレンソルビトールモノステアレート等のポリオキシエチレンソルビトール脂肪酸エステル;ポリオキシエチレンメチルグルコシド脂肪酸エステル;ポリオキシエチレンアルキルエーテル脂肪酸エステル;ポリオキシエチレンソルビトールミツロウ等のポリオキシエチレン動植物油脂類;イソステアリルグリセリルエーテル、キミルアルコール、セラキルアルコール、バチルアルコール等のアルキルグリセリルエーテル類;多価アルコールアルキルエーテル;ポリオキシエチレンアルキルアミン;テトラポリオキシエチレン・テトラポリオキシプロピレン−エチレンジアミン縮合物類;サポニン、ソホロリピッド等の天然系界面活性剤;ポリオキシエチレン脂肪酸アミド;ヤシ油脂肪酸モノエタノールアミド(コカミドMEA)、ヤシ油脂肪酸ジエタノールアミド(コカミドDEA)、ラウリン酸モノエタノールアミド(ラウラミドMEA)、ラウリン酸ジエタノールアミド(ラウラミドDEA)、ラウリン酸モノイソプロパノールアミド(ラウラミドMIPA)、パルミチン酸モノエタノールアミド(パルタミドMEA)、パルミチン酸ジエタノールアミド(パルタミドDEA)、ヤシ油脂肪酸メチルエタノールアミド(コカミドメチルMEA)等の脂肪酸アルカノールアミド類;ラウラミンオキシド、コカミンオキシド、ステアラミンオキシド、ベヘナミンオキシド等のアルキルジメチルアミンオキシド;アルキルエトキシジメチルアミンオキシド;ポリオキシエチレンアルキルメルカプタン;ジメチコンコポリオール等のポリエーテル変性シリコーン、ポリシロキサン・オキシアルキレン共重合体、ポリグリセリン変性シリコーン、糖変性シリコーン等のシリコーン系非イオン性界面活性剤;などが挙げられる。 Examples of the nonionic surfactant include laures (polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steares (polyoxyethylene stearyl ether), behenes (polyoxyethylene behenyl ether), and the like. Polyoxyethylene alkyl ethers with various polyoxyethylene additions such as isosteares (polyoxyethylene isostearyl ethers) and octyldodeces (polyoxyethylene octyldodecyl ethers); polyoxyethylene alkylphenyl ethers; Oil, polyoxyethylene castor oil, polyoxyethylene cured castor oil monoisostearate, polyoxyethylene cured castor oil triisostearate, polyoxyethylene cured castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene cured castor oil Hima oil such as maleic acid and hardened Hima oil derivative; polyoxyethylene phytosterol; polyoxyethylene cholesterol; polyoxyethylene cholestanol; polyoxyethylene lanolin; polyoxyethylene reduced lanolin; polyoxyethylene / polyoxypropylene cetyl ether, poly Polyoxyethylene poly such as oxyethylene / polyoxypropylene 2-decyltetradecyl ether, polyoxyethylene / polyoxypropylene monobutyl ether, polyoxyethylene / polyoxypropylene hydrogenated lanolin, polyoxyethylene / polyoxypropylene glycerin ether, etc. Oxypropylene alkyl ether; polyoxyethylene / polyoxypropylene glycol; (poly) glycerin polyoxypropylene glycol such as PPG-9 diglyceryl; glyceryl stearate, glyceryl isostearate, glyceryl palmitate, glyceryl myristate, glyceryl oleate, Glycerin fatty acid partial esters such as coconut oil fatty acid glyceryl, monocotton seed oil fatty acid glycerin, monoercaate glycerin, sesquioleate glycerin, α, α'-pyroglutamate oleate glycerin, monostearate glycerin malic acid; polyglyceryl-2, 3, 4, 5, 6, 8, 8, 10, polyglyceryl distearate-6, 10, polyglyceryl tristearate-2, polyglyceryl decastarate-10, isosteari Polyglyceryl-2, 3, 4, 4, 5, 6, 8, 10, 10 polyglyceryl diisostearate-2 (diglyceryl diisostearate), 3, 10, 10, polyglyceryl triisostearate-2, tetra Polyglyceryl-2 isostearate, polyglyceryl-10 decaisostearate, polyglyceryl-2 oleate, 3, 4, 5, 5, 6, 8, 10, dioleate polyglyceryl-6, polyglyceryl trioleate-2, Polyglycerin fatty acid ester such as polyglyceryl-10 decaoleate; ethylene glycol monofatty acid ester such as ethylene glycol monostearate; propylene glycol monofatty acid ester such as propylene glycol monostearate; pentaerythritol partial fatty acid ester; sorbitol partial fatty acid ester; mulch Thor partial fatty acid ester; polysorbate ether; sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexylate Polysorbate fatty acid esters such as diglycerol sorbitan and diglycerol sorbitan tetra-2-ethylhexylate; sugar derivative partial esters such as sucrose fatty acid ester, methyl glucoside fatty acid ester, trehalose undecylate; alkyl glucoside such as caprylyl glucoside; alkyl polyglycoside Lanoline alcohol; Reduced lanolin; Polyoxyethylene fatty acid mono and diesters such as polyoxyethylene distearate, polytylene glycol diisostearate, polyoxyethylene monooleate, and polyoxyethylene dioleate; polyoxyethylene propylene Glycol fatty acid ester; Polyoxyethylene glycerin monostearate, polyoxyethylene glycerin monoisostearate, polyoxyethylene glycerin triisostearate and other polyoxyethylene glycerin fatty acid esters; polyoxyethylene sorbitan Polyoxyethylene sorbitan fatty acid esters such as monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tetraoleate; polyoxy Polyoxyethylene sorbitol fatty acid esters such as ethylene sorbitol monolaurate, polyoxyethylene sorbitol monooleate, polyoxyethylene sorbitol pentaoleate, polyoxyethylene sorbitol monostearate; polyoxyethylene sorbitol fatty acid esters; polyoxyethylene alkyl Ether fatty acid esters; Polyoxyethylene animal and vegetable fats and oils such as polyoxyethylene sorbitol honey; Alkyl glyceryl ethers such as isostearyl glyceryl ethers, chimyl alcohols, ceracyl alcohols, and batyl alcohols; Polyhydric alcohol alkyl ethers; Polyoxyethylene alkyls Amin; Tetrapolyoxyethylene / Tetrapolyoxypropylene-ethylenediamine condensates; Natural surfactants such as saponin and sophorolipid; Polyoxyethylene fatty acid amide; Palm oil fatty acid monoethanolamide (cocamide MEA), Palm oil fatty acid diethanolamide (Cocamide DEA), Laurate Monoethanolamide (Lauramide MEA), Laurate Diethanolamide (Lauramide DEA), Lauric Acid Monoisopropanolamide (Lauramide MIPA), Palmitic Acid Monoethanolamide (Partamide MEA), Palmitate Diethanolamide (Partamide DEA), fatty acid alkanolamides such as coconut oil fatty acid methylethanolamide (cocamidomethyl MEA); alkyldimethylamine oxides such as lauramine oxide, cocamine oxide, stearamine oxide, behenamine oxide; alkylethoxydimethylamine oxide; poly Oxyethylene alkyl mercaptans; polyether-modified silicones such as dimethicone copolyol, polysiloxane / oxyalkylene copolymers, polyglycerin-modified silicones, sugar-modified silicones and other silicone-based nonionic surfactants; and the like.
陽イオン性界面活性剤としては、例えば、ベヘントリモニウムクロリド、ステアルトリモニウムクロリド、セトリモニウムクロリド、ラウリルトリモニウムクロリド等のアルキルトリメチルアンモニウムクロリド;ステアリルトリモニウムブロミド等のアルキルトリメチルアンモニウムブロミド;ジステアリルジモニウムクロリド、ジココジモニウムクロリド等のジアルキルジメチルアンモニウムクロリド;ステアラミドプロピルジメチルアミン、ステアラミドエチルジエチルアミン等の脂肪酸アミドアミンおよびその塩;ステアロキシプロピルジメチルアミン等のアルキルエーテルアミンおよびその塩または四級塩;エチル硫酸長鎖分岐脂肪酸(12〜31)アミノプロピルエチルジメチルアンモニウム、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム等の脂肪酸アミド型四級アンモニウム塩;ポリオキシエチレンアルキルアミンおよびその塩または四級塩;アルキルアミン塩;脂肪酸アミドグアニジウム塩;アルキルエーテルアミンモニウム塩;アルキルトリアルキレングリコールアンモニウム塩;ベンザルコニウム塩;ベンゼトニウム塩;塩化セチルピリジニウム等のピリジニウム塩;イミダゾリニウム塩;アルキルイソキノリニウム塩;ジアルキルモリホニウム塩;ポリアミン脂肪酸誘導体;アミノプロピルジメチコンおよびアモジメチコン等のアミノ変性シリコーン、カチオン変性シリコーン、カチオン変性およびポリエーテル変性シリコーン、アミノ変性およびポリエーテル変性シリコーン等のシリコーン系陽イオン性界面活性剤;などが挙げられる。 Examples of the cationic surfactant include alkyltrimethylammonium chlorides such as behentrimonium chloride, stealtrimonium chloride, cetrimonium chloride, and lauryltrimonium chloride; alkyltrimethylammonium bromides such as stearyltrimonium bromide; and distearyldi. Dialkyldimethylammonium chlorides such as monium chloride and dicocodimonium chloride; fatty acid amide amines such as stearamide propyl dimethylamine and stearamide ethyl diethyl amine and salts thereof; alkyl ether amines such as stearoxypropyl dimethylamine and salts or quaternary salts thereof; Ethylsulfate long chain branched fatty acids (12-31) Aminopropyl ethyldimethylammonium, Lanolin fatty acid ethyl sulfate Aminopropyl ethyldimethylammonium and other fatty acid amide-type quaternary ammonium salts; polyoxyethylene alkylamines and their salts or quaternary salts; alkyl Amine salt; fatty acid amide guanidium salt; alkyl ether amine monium salt; alkyltrialkylene glycol ammonium salt; benzalconium salt; benzethonium salt; pyridinium salt such as cetylpyridinium chloride; imidazolinium salt; alkylisoquinolinium salt Dialkylmoriphonium salts; Polyamine fatty acid derivatives; Amino-modified silicones such as aminopropyldimethicone and amodimethicone, cationic-modified silicones, cationic-modified and polyether-modified silicones, amino-modified and polyether-modified silicones and other silicone-based cationic interfaces. Activators; and the like.
両性界面活性剤としては、例えば、ラウリルベタイン(ラウリルジメチルアミノ酢酸ベタイン)等のN−アルキル−N,N−ジメチルアミノ酸ベタイン;コカミドプロピルベタイン、ラウラミドプロピルベタイン等の脂肪酸アミドアルキル−N,N−ジメチルアミノ酸ベタイン;ココアンホ酢酸ナトリウム、ラウロアンホ酢酸ナトリウム等のイミダゾリン型ベタイン;アルキルジメチルタウリン等のアルキルスルホベタイン;アルキルジメチルアミノエタノール硫酸エステル等の硫酸型ベタイン;アルキルジメチルアミノエタノールリン酸エステル等のリン酸型ベタイン;ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルセリン、スフィンゴミエリン等のスフィンゴリン脂質、リゾレシチン、水素添加大豆リン脂質、部分水素添加大豆リン脂質、水素添加卵黄リン脂質、部分水素添加卵黄リン脂質、水酸化レシチン等のリン脂質類;シリコーン系両性界面活性剤;などが挙げられる。 Examples of the amphoteric surfactant include N-alkyl-N, N-dimethylamino acid betaine such as lauryl betaine (lauryl dimethylaminoacetic acid betaine); fatty acid amide alkyl-N, N such as cocamidopropyl betaine and lauramide propyl betaine. -Dimethyl amino acid betaine; imidazoline-type betaine such as sodium cocoamphoacetate and sodium lauroamphoacetate; alkylsulfobetaine such as alkyldimethyltaurin; sulfate-type betaine such as alkyldimethylaminoethanol sulfate; phosphoric acid such as alkyldimethylaminoethanol phosphate Type betaine; phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingomyelin and other sphingolin lipids, lysolecithin, hydrogenated soybean phospholipid, partially hydrogenated soybean phospholipid, hydrogenated egg yolk phospholipid, partially hydrogenated egg yolk phospholipid, hydroxylation Phosphorlipids such as lecithin; silicone-based amphoteric surfactants; and the like.
高分子界面活性剤としては、例えば、ポリビニルアルコール、アルギン酸ナトリウム、デンプン誘導体、トラガントガム、アクリル酸・メタアクリル酸アルキル共重合体;シリコーン系各種界面活性剤;などが挙げられる。 Examples of the polymer surfactant include polyvinyl alcohol, sodium alginate, starch derivatives, tragant gum, acrylic acid / alkyl methacrylic acid copolymers; various silicone-based surfactants; and the like.
高分子、増粘剤、およびゲル化剤としては、例えば、グアーガム、ローカストビーンガム、クィーンスシード、カラギーナン、ガラクタン、アラビアガム、タラガム、タマリンド、ファーセレラン、カラヤガム、トロロアオイ、キャラガム、トラガントガム、ペクチン、ペクチン酸およびそのナトリウム塩等の塩、アルギン酸およびそのナトリウム塩等の塩、マンナン;コメ、トウモロコシ、バレイショ、コムギ等のデンプン;キサンタンガム、デキストラン、サクシノグルカン、カードラン、ヒアルロン酸およびその塩、ザンサンガム、プルラン、ジェランガム、キチン、キトサン、寒天、カッソウエキス、コンドロイチン硫酸塩、カゼイン、コラーゲン、ゼラチン、アルブミン;メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロースおよびそのナトリウム等の塩、メチルヒドロキシプロピルセルロース、セルロース硫酸ナトリウム、ジアルキルジメチルアンモニウム硫酸セルロース、結晶セルロース、セルロース末等のセルロースおよびその誘導体;可溶性デンプン、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン、メチルデンプン等のデンプン系高分子、塩化ヒドロキシプロピルトリモニウムデンプン、オクテニルコハク酸トウモロコシデンプンアルミニウム等のデンプン誘導体;アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等アルギン酸誘導体;ポリビニルピドリドン(PVP)、ポリビニルアルコール(PVA)、ビニルピドリドン・ビニルアルコール共重合体、ポリビニルメチルエーテル;ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレン・ポリオキシプロピレン共重合体;(メタクリロイルオキシエチルカルボキシベタイン/メタクリル酸アルキル)コポリマー、(アクリレーツ/アクリル酸ステアリル/メタクリル酸エチルアミンオキシド)コポリマー等の両性メタクリル酸エステル共重合体;(ジメチコン/ビニルジメチコン)クロスポリマー、(アクリル酸アルキル/ジアセトンアクリルアミド)コポリマー、(アクリル酸アルキル/ジアセトンアクリルアミド)コポリマーAMP;ポリ酢酸ビニル部分けん化物、マレイン酸共重合体;ビニルピロリドン・メタクリル酸ジアルキルアミノアルキル共重合体;アクリル樹脂アルカノールアミン;ポリエステル、水分散性ポリエステル;ポリアクリルアミド;ポリアクリル酸エチル等のポリアクリル酸エステル共重合体、カルボキシビニルポリマー、ポリアクリル酸およびそのナトリウム塩等の塩、アクリル酸・メタアクリル酸エステル共重合体;アクリル酸・メタアクリル酸アルキル共重合体;ポリクオタニウム−10等のカチオン化セルロース、ポリクオタニウム−7等のジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体、ポリクオタニウム−22等のアクリル酸・ジアリルジメチルアンモニウムクロリド共重合体、ポリクオタニウム−39等のアクリル酸・ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体、アクリル酸・カチオン化メタアクリル酸エステル共重合体、アクリル酸・カチオン化メタアクリル酸アミド共重合体、ポリクオタニウム−47等のアクリル酸・アクリル酸メチル・塩化メタクリルアミドプロピルトリメチルアンモニウム共重合体、塩化メタクリル酸コリンエステル重合体;カチオン化オリゴ糖、カチオン化デキストラン、グアーヒドロキシプロピルトリモニウムクロリド等のカチオン化多糖類;ポリエチレンイミン;カチオンポリマー;ポリクオタニウム−51等の2−メタクリロイルオキシエチルホスホリルコリンの重合体およびメタクリル酸ブチル共重合体等との共重合体;アクリル樹脂エマルジョン、ポリアクリル酸エチルエマルジョン、ポリアクリルアルキルエステルエマルジョン、ポリ酢酸ビニル樹脂エマルジョン、天然ゴムラテックス、合成ラテックス等の高分子エマルジョン;ニトロセルロース;ポリウレタン類および各種共重合体;各種シリコーン類;アクリル−シリコーングラフト共重合体等のシリコーン系各種共重合体;各種フッ素系高分子;12−ヒドロキシステアリン酸およびその塩;パルミチン酸デキストリン、ミリスチン酸デキストリン等のデキストリン脂肪酸エステル;無水ケイ酸、煙霧状シリカ(超微粒子無水ケイ酸)、ケイ酸アルミニウムマグネシウム、ケイ酸ナトリウムマグネシウム、金属石鹸、ジアルキルリン酸金属塩、ベントナイト、ヘクトライト、有機変性粘土鉱物、ショ糖脂肪酸エステル、フラクトオリゴ糖脂肪酸エステル;などが挙げられる。 Polymers, thickeners, and gelling agents include, for example, guar gum, locust bean gum, queens seed, carrageenan, galactan, arabic gum, tara gum, tamarind, farcerelan, karaya gum, trolley aoi, cara gum, tragant gum, pectin, pectin. Salts such as acid and its sodium salt, salts such as alginic acid and its sodium salt, mannan; starches such as rice, corn, potatoes, wheat; xanthan gum, dextran, succinoglucan, curdran, hyaluronic acid and its salts, zansan gum, Purulan, gellan gum, chitin, chitosan, agar, casso extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and salts such as sodium thereof, methyl hydroxypropyl cellulose, cellulose Cellulose such as sodium sulfate, dialkyldimethylammonium sulfate cellulose, crystalline cellulose, cellulose powder and derivatives thereof; starch-based polymers such as soluble starch, carboxymethyl starch, methylhydroxypropyl starch and methyl starch, hydroxypropyltrimonium chloride starch, octenyl succinate. Acid corn starch Detergents such as aluminum; alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyridone (PVP), polyvinyl alcohol (PVA), vinylpyridone / vinyl alcohol copolymer, polyvinylmethyl ether; polyethylene glycol, polypropylene glycol , Polyoxyethylene / polyoxypropylene copolymer; (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (Acrylate / stearyl acrylate / ethylamine methacrylate) copolymer and other amphoteric methacrylic acid ester copolymer; (dimethicone) / Vinyl dimethicone) crosspolymer, (alkyl acrylate / diacetoneacrylamide) copolymer, (alkyl acrylate / diacetoneacrylamide) copolymer AMP; polyvinyl acetate partially saponified product, maleic acid copolymer; vinylpyrrolidone / dialkylamino methacrylate Alkyl copolymer; acrylic resin alkanolamine; polyeste , Water-dispersible polyester; polyacrylamide; polyacrylic acid ester copolymer such as ethyl polyacrylate, carboxyvinyl polymer, salt such as polyacrylic acid and sodium salt thereof, acrylic acid / methacrylic acid ester copolymer; Acrylic acid / alkyl methacrylic acid copolymer; cationized cellulose such as polyquaternium-10, diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-7, acrylic acid / diallyldimethylammonium chloride copolymer such as polyquaternium-22. , Polyquaternium-39 and other acrylic acid / diallyldimethylammonium chloride / acrylamide copolymers, acrylic acid / cationized metaacrylic acid ester copolymers, acrylic acid / cationized metaacrylic acid amide copolymers, polyquaternium-47 and the like. Acrylic acid / methyl acrylate / methacrylic acid propyltrimethylammonium copolymer, choline methacrylate polymer; cationized polysaccharides such as cationized oligosaccharide, cationized dextran, guarhydroxypropyltrimonium chloride; polyethyleneimine; Cationic polymer; polymer of 2-methacryloyloxyethyl phosphorylcholine such as polyquaternium-51 and polymer with butyl methacrylate copolymer and the like; acrylic resin emulsion, ethyl polyacrylate emulsion, polyacrylic alkyl ester emulsion, vinyl acetate Polymer emulsions such as resin emulsions, natural rubber latex, synthetic latex; nitrocellulose; polyurethanes and various copolymers; various silicones; various silicone-based copolymers such as acrylic-silicone graft copolymers; various fluoropolymers; Polymers; 12-hydroxystearic acid and salts thereof; dextrin fatty acid esters such as dextrin palmitate and dextrin myristinate; silicic anhydride, fuming silica (ultrafine anhydrous silicic acid), aluminum magnesium silicate, magnesium sodium silicate, metal Examples thereof include soaps, dialkyl phosphate metal salts, bentonite, hectolite, organically modified clay minerals, sucrose fatty acid esters, fructo-oligosaccharide fatty acid esters; and the like.
溶剤および噴射剤類としては、例えば、エタノール、2−プロパノール(イソプロピルアルコール)、ブタノール、イソブチルアルコール等の低級アルコール類;プロピレングリコール、1,3−ブチレングリコール、ジエチレングリコール、ジプロピレングリコール、イソペンチルジオール等のグリコール類;ジエチレングリコールモノエチルエーテル(エトキシジグリコール)、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル等のグリコールエーテル類;エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のグリコールエーテルエステル類;コハク酸ジエトキシエチル、エチレングリコールジサクシネート等のグリコールエステル類;ベンジルアルコール、ベンジルオキシエタノール、炭酸プロピレン、炭酸ジアルキル、アセトン、酢酸エチル、N−メチルピロリドン;トルエン;フルオロカーボン、次世代フロン;LPG、ジメチルエーテル、炭酸ガス等の噴射剤;などが挙げられる。 Examples of the solvent and propellant include lower alcohols such as ethanol, 2-propanol (isopropyl alcohol), butanol and isobutyl alcohol; propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, isopentyldiol and the like. Glycols: Diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoethyl ether, dipropylene glycol mono Glycol ethers such as ethyl ether; glycol ether esters such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and propylene glycol monoethyl ether acetate; glycol esters such as diethoxyethyl succinate and ethylene glycol disuccinate Benzyl alcohol, benzyl oxyethanol, propylene carbonate, dialkyl carbonate, acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbon, next-generation freon; propellants such as LPG, dimethyl ether, carbon dioxide gas; and the like.
酸化防止剤としては、例えば、トコフェロール(ビタミンE)、酢酸トコフェロール等のトコフェロール誘導体;BHT、BHA;没食子酸プロピル等の没食子酸誘導体;ビタミンC(アスコルビン酸)およびその誘導体;エリソルビン酸およびその誘導体;亜硫酸ナトリウム等の亜硫酸塩;亜硫酸水素ナトリウム等の亜硫酸水素塩;チオ硫酸ナトリウム等のチオ硫酸塩;メタ亜硫酸水素塩;チオタウリン、ヒポタウリン;チオグリセロール、チオ尿素、チオグリコール酸、システイン塩酸塩;などが挙げられる。 Examples of the antioxidant include tocopherol derivatives such as tocopherol (vitamin E) and tocopherol acetate; BHT, BHA; gallic acid derivatives such as propyl gallate; vitamin C (ascorbic acid) and its derivatives; erythorbic acid and its derivatives; Sulfites such as sodium sulfite; hydrogen sulfites such as sodium hydrogen sulfite; thiosulfites such as sodium thiosulfite; metahydrosulfites; thiotaurine, hypotaurine; thioglycerol, thiourea, thioglycolic acid, cysteine hydrochloride; etc. Can be mentioned.
還元剤としては、例えば、チオグリコール酸、システイン、システアミンなどが挙げられる。 Examples of the reducing agent include thioglycolic acid, cysteine, cysteamine and the like.
酸化剤としては、例えば、過酸化水素水、過硫酸アンモニウム、臭素酸ナトリウム、過炭酸などが挙げられる。 Examples of the oxidizing agent include hydrogen peroxide solution, ammonium persulfate, sodium bromate, and percarbonate.
防腐剤および抗菌剤としては、例えば、メチルパラベン、エチルパラベン、プロピルパラベン、ブチルパラベン等のヒドロキシ安息香酸およびその塩若しくはそのエステル;サリチル酸;安息香酸ナトリウム;フェノキシエタノール;1,2−ペンタンジオール、1,2−ヘキサンジオール等の1,2−ジオール;メチルクロロイソチアゾリノン、メチルイソチアゾリノン等のイソチアゾリンオン誘導体;イミダゾリニウムウレア;デヒドロ酢酸およびその塩;フェノール類;トリクロサン等のハロゲン化ビスフェノール類、酸アミド類、四級アンモニウム塩類;トリクロロカルバニド、ジンクピリチオン、塩化ベンザルコニウム、塩化ベンゼトニウム、ソルビン酸、クロルヘキシジン、グルコン酸クロルヘキシジン、ハロカルバン、ヘキサクロロフェン、ヒノキチオール;フェノール、イソプロピルフェノール、クレゾール、チモール、パラクロロフェノール、フェニルフェノール、フェニルフェノールナトリウム等のその他フェノール類;フェニルエチルアルコール、感光素類、抗菌性ゼオライト、銀イオン;などが挙げられる。 Examples of preservatives and antibacterial agents include hydroxybenzoic acids such as methylparaben, ethylparaben, propylparaben and butylparaben and salts thereof or esters thereof; salicylic acid; sodium benzoate; phenoxyethanol; 1,2-pentanediol, 1,2. 1,2-diols such as −hexanediol; isothiazolinone derivatives such as methylchloroisothiazolinone and methylisothiazolinone; imidazolinium urea; dehydroacetic acid and salts thereof; phenols; halogenated bisphenols such as triclosan, acids Amidos, quaternary ammonium salts; trichlorocarbanide, zincpyrythion, benzalkonium chloride, benzethonium chloride, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban, hexachlorophene, hinokithiol; phenol, isopropylphenol, cresol, timol, parachloro Other phenols such as phenol, phenylphenol and sodium phenylphenol; phenylethyl alcohol, photosensitizers, antibacterial zeolite, silver ion; and the like can be mentioned.
キレート剤としては、例えば、EDTA、EDTA2Na、EDTA3Na、EDTA4Na等のエデト酸塩(エチレンジアミン四酢酸塩);HEDTA3Na等のヒドロキシエチルエチレンジアミン三酢酸塩;ペンテト酸塩(ジエチレントリアミン五酢酸塩);フィチン酸;エチドロン酸等のホスホン酸およびそのナトリウム塩等の塩類;シュウ酸ナトリウム;ポリアスパラギン酸、ポリグルタミン酸等のポリポリアミノ酸類;ポリリン酸ナトリウム、メタリン酸ナトリウム、リン酸;クエン酸ナトリウム、クエン酸、アラニン、ジヒドロキシエチルグリシン、グルコン酸、アスコルビン酸、コハク酸、酒石酸;などが挙げられる。 Examples of the chelating agent include edetates (ethylenediaminetetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediaminetriacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytate; ethidron. Phosphonic acid such as acid and salts such as sodium salt thereof; sodium oxalate; polypolyamino acids such as polyaspartic acid and polyglutamic acid; sodium polyphosphate, sodium metaphosphate, phosphoric acid; sodium citrate, citric acid, alanine, dihydroxy Ethylglycine, gluconic acid, ascorbic acid, succinic acid, tartaric acid; and the like.
pH調整剤、酸、およびアルカリとしては、例えば、クエン酸、クエン酸ナトリウム、乳酸、乳酸ナトリウム、グリコール酸、コハク酸、酢酸、酢酸ナトリウム、リンゴ酸、酒石酸、フマル酸、リン酸、塩酸、硫酸、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、イソプロパノールアミン、トリイソプロパノールアミン、2−アミノ−2−メチル−1,3ープロパンジオール、2−アミノ−2−ヒドロキシメチル−1,3ープロパンジオール、アルギニン、水酸化ナトリウム、水酸化カリウム、アンモニア水、炭酸グアニジン、炭酸アンモニウムなどが挙げられる。 Examples of pH adjusters, acids, and alkalis include citric acid, sodium citrate, lactic acid, sodium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, malic acid, tartrate acid, fumaric acid, phosphoric acid, hydrochloric acid, sulfuric acid. , Monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine , Sodium hydroxide, potassium hydroxide, aqueous ammonia, guanidine carbonate, ammonium carbonate and the like.
粉体類としては、例えば、マイカ、タルク、カオリン、セリサイト、モンモリロナイト、カオリナイト、雲母、白雲母、金雲母、合成雲母、紅雲母、黒雲母、パーミキュライト、炭酸マグネシウム、炭酸カルシウム、ケイ酸アルミニウム、ケイ酸バリウム、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸ストロンチウム、タングステン酸金属塩、マグネシウム、ゼオライト、硫酸バリウム、焼成硫酸カルシウム、リン酸カルシウム、弗素アパタイト、ヒドロキシアパタイト、セラミックパウダー、ベントナイト、スメクタイト、粘土、泥、金属石鹸(例えば、ミリスチン酸亜鉛、パルミチン酸カルシウム、ステアリン酸アルミニウム)、炭酸カルシウム、ベンガラ、黄酸化鉄、黒酸化鉄、群青、紺青、カーボンブラック、酸化チタン、微粒子および超微粒子酸化チタン、酸化亜鉛、微粒子および超微粒子酸化亜鉛、アルミナ、シリカ、煙霧状シリカ(超微粒子無水ケイ酸)、雲母チタン、魚鱗箔、窒化ホウ素、ホトクロミック顔料、合成フッ素金雲母、微粒子複合粉体、金、アルミニウム等の各種の大きさ・形状の無機粉体、および、これらをハイドロジェンシリコーン、環状ハイドロジェンシリコーン等のシリコーンまたはその他のシランまたはチタンカップリング剤等の各種表面処理剤で処理を行って疎水化または親水化した粉体等の無機粉体;デンプン、セルロース、ナイロンパウダー、ポリエチレン末、ポリメタクリル酸メチル末、ポリスチレン末、スチレンとアクリル酸の共重合体樹脂粉末、ポリエステル末、ベンゾグアナミン樹脂粉末、ポリエチレンテレフタレート・ポリメチルメタクリレート積層末、ポリエチレンテレフタレート・アルミニウム・エポキシ積層末等、ウレタン粉末、シリコーン粉末、テフロン(登録商標)粉末等の各種の大きさ・形状の有機系粉体、表面処理粉体、および有機無機複合粉体;などが挙げられる。 Examples of powders include mica, talc, kaolin, cericite, montmorillonite, kaolinite, mica, white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate. , Barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungrate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, Mud, metal soap (eg zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, dark blue, carbon black, titanium oxide, fine particles and ultrafine titanium oxide, Zinc oxide, fine particles and ultrafine particles Zinc oxide, alumina, silica, fumigant silica (ultrafine particles anhydrous silicic acid), mica titanium, fish scale foil, boron nitride, photochromic pigment, synthetic fluorine gold mica, fine particle composite powder, gold, Inorganic powder of various sizes and shapes such as aluminum, and these are treated with silicone such as hydrogen silicone and cyclic hydrogen silicone or other surface treatment agents such as silane or titanium coupling agent to be hydrophobic. Inorganic powder such as powder made or hydrophilized; starch, cellulose, nylon powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene and acrylic acid copolymer resin powder, polyester powder, benzoguanamine resin powder, Organic powders of various sizes and shapes such as polyethylene terephthalate / polymethylmethacrylate laminated powders, polyethylene terephthalates / aluminum / epoxy laminated powders, urethane powders, silicone powders, Teflon (registered trademark) powders, surface treatment powders, etc. And organic-inorganic composite powder; and the like.
無機塩としては、例えば、食塩、並塩、岩塩、海塩、天然塩等の塩化ナトリウム含有塩類;塩化カリウム、塩化アルミニウム、塩化カルシウム、塩化マグネシウム、にがり、塩化亜鉛、塩化アンモニウム;硫酸ナトリウム、硫酸アルミニウム、硫酸アルミニウム・カリウム(ミョウバン)、硫酸アルミニウム・アンモニウム、硫酸バリウム、硫酸カルシウム、硫酸カリウム、硫酸マグネシウム、硫酸亜鉛、硫酸鉄、硫酸銅;リン酸1Na・2Na・3Na等のリン酸ナトリウム類、リン酸カリウム類、リン酸カルシウム類、リン酸マグネシウム類;などが挙げられる。 Examples of inorganic salts include sodium chloride-containing salts such as salt, normal salt, rock salt, sea salt, and natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, sardine, zinc chloride, ammonium chloride; sodium sulfate, sulfate. Aluminum, aluminum / potassium sulfate (myoban), aluminum / ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na / 2Na / 3Na phosphate, Examples thereof include potassium phosphates, calcium phosphates, magnesium phosphates; and the like.
紫外線吸収剤としては、例えば、パラアミノ安息香酸、パラアミノ安息香酸モノグリセリンエステル、N,N−ジプロポキシパラアミノ安息香酸エチルエステル、N,N−ジエトキシパラアミノ安息香酸エチルエステル、N,N−ジメチルパラアミノ安息香酸エチルエステル、N,N−ジメチルパラアミノ安息香酸ブチルエステル、N,N−ジメチルパラアミノ安息香酸エチルエステル等の安息香酸系紫外線吸収剤;ホモメンチル−N−アセチルアントラニレート等のアントラニル酸系紫外線吸収剤;サリチル酸およびそのナトリウム塩、アミルサリシレート、メンチルサリシレート、ホモメンチルサリシレート、オクチルサリシレート、フェニルサリシレート、ベンジルサリシレート、p−イソプロパノールフェニルサリシレート等のサリチル酸系紫外線吸収剤;オクチルシンナメート、エチル−4−イソプロピルシンナメート、メチル−2,5−ジイソプロピルシンナメート、エチル−2,4−ジイソプロピルシンナメート、メチル−2,4−ジイソプロピルシンナメート、プロピル−p−メトキシシンナメート、イソプロピル−p−メトキシシンナメート、イソアミル−p−メトキシシンナメート、2−エチルヘキシルp−メトキシシンナメート(パラメトキシケイヒ酸オクチル)、2−エトキシエチル−p−メトキシシンナメート(シノキサート)、シクロヘキシル−p−メトキシシンナメート、エチル−α−シアノ−β−フェニルシンナメート、2−エチルヘキシルα−シアノ−β−フェニルシンナメート(オクトクリン)、グリセリルモノ−2−エチルヘキサノイル−ジパラメトキシシンナメート、フェルラ酸およびその誘導体等の桂皮酸系紫外線吸収剤;2,4−ジヒドロキシベンゾフェノン、2,2’− ジヒドロキシ−4−メトキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、2−ヒドロキシ−4− メトキシベンゾフェノン(オキシベンゾン−3)、2−ヒドロキシ−4−メトキシ−4’−メチルベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸塩、4−フェニルベンゾフェノン、2−エチルヘキシル−4’−フェニル−ベンゾフェノン−2−カルボキシレート、2−ヒドロキシ−4−n−オクトキシベンゾフェノン、4−ヒドロキシ−3−カルボキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤;3−(4’−メチルベンジリデン)−d,l−カンファー、3−ベンジリデン−d,l−カンファー;2−フェニル−5−メチルベンゾキサゾール;2,2’−ヒドロキシ−5−メチルフェニルベンゾトリアゾール;2−(2’−ヒドロキシ−5’−t−オクチルフェニル)ベンゾトリアゾール;2−(2’−ヒドロキシ−5’−メチルフェニルベンゾトリアゾール;ジベンザラジン;ジアニソイルメタン;5−(3,3−ジメチル−2−ノルボルニリデン)−3−ペンタン−2−オン;4−t−ブチルメトキシジベンゾイルメタン等のジベンゾイルメタン誘導体;オクチルトリアゾン;ウロカニン酸およびウロカニン酸エチル等のウロカニン酸誘導体;2−(2'−ヒドロキシ−5'−メチルフェニル)ベンゾトリアゾール、1−(3,4−ジメトキシフェニル)−4,4−ジメチル−1,3−ペンタンジオン、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸2−エチルヘキシル等のヒダントイン誘導体、フェニルベンズイミダソゾールスルホン酸、テレフタリリデンジカンフルスルホン酸、ドロメトリゾールトリシロキサン、アントラニル酸メチル、ルチンおよびその誘導体、オリザノールおよびその誘導体;などが挙げられる。 Examples of the ultraviolet absorber include paraaminobenzoic acid, paraaminobenzoic acid monoglycerin ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl ester, N, N-dimethylparaaminobenzoic acid. An benzoic acid-based ultraviolet absorber such as acid ethyl ester, N, N-dimethylparaaminobenzoic acid butyl ester, N, N-dimethylparaaminobenzoic acid ethyl ester; anthranyl acid-based ultraviolet absorber such as homomentyl-N-acetylanthranilate. Salicylic acid-based ultraviolet absorbers such as salicylic acid and its sodium salt, amylsalicylate, menthylsalicylate, homomentylsalicylate, octylsalicylate, phenylsalicylate, benzylsalicylate, p-isopropanol phenylsalicylate; octylcinnamate, ethyl-4-isopropylcinnamete , Methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p -Methoxycinnamate, 2-ethylhexyl p-methoxycinnamate (octyl paramethoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate (synoxate), cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β Ceramic acid-based UV absorbers such as -phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate (octocrine), glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate, ferulic acid and its derivatives; 2,4-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone (oxybenzon-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl- 4'-Phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. Benzophenone UV absorbers; 3- (4'-methylbenzylidene) -d, l-phenyl, 3-benziliden-d, l-phenyl; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy -5-Methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoilmethane; 5 -(3,3-Dimethyl-2-norbornylidene) -3-pentan-2-one; dibenzoylmethane derivatives such as 4-t-butylmethoxydibenzoylmethane; octylriazone; urocanine such as urocanic acid and ethyl urocanate Acid derivatives; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentandione, dimethoxybenzidenedioxoimidazolidine Hydantin derivatives such as 2-ethylhexyl propionate, phenylbenzimidazole sulfonic acid, terephthalylidenedicanfursulfonic acid, drometrizole trisiloxane, methyl anthranilate, rutin and its derivatives, oryzanol and its derivatives; and the like. ..
美白剤としては、例えば、アルブチン、α−アルブチン等のヒドロキノン配糖体およびそのエステル類;アスコルビン酸、アスコルビン酸リン酸エステルナトリウム塩およびアスコルビン酸リン酸エステルマグネシウム塩等のアスコルビン酸リン酸エステル塩、アスコルビン酸テトライソパルミチン酸エステル等のアスコルビン酸脂肪酸エステル、アスコルビン酸エチルエーテル等のアスコルビン酸アルキルエーテル、アスコルビン酸−2−グルコシド等のアスコルビン酸グルコシドおよびその脂肪酸エステル類、アスコルビン酸硫酸エステル、リン酸トコフェリルアスコルビル等のアスコルビン酸誘導体;コウジ酸、エラグ酸、トラネキサム酸およびその誘導体、フェルラ酸およびその誘導体、プラセンタエキス、グルタチオン、オリザノール、ブチルレゾルシノール、油溶性カモミラエキス、油溶性カンゾウエキス、西河柳エキス、ユキノシタエキス等植物エキス;などが挙げられる。 Examples of the whitening agent include hydroquinone glycosides such as albutin and α-albutin and their esters; ascorbic acid phosphate ester salts such as ascorbic acid, ascorbic acid phosphate sodium salt and ascorbic acid phosphate ester magnesium salt, and the like. Ascorbic acid fatty acid ester such as ascorbic acid tetraisopalmitic acid ester, ascorbic acid alkyl ether such as ascorbic acid ethyl ether, ascorbic acid glucoside such as ascorbic acid-2-glucoside and its fatty acid esters, ascorbic acid sulfate ester, phosphate toco Ascorbic acid derivatives such as ferryl ascorvir; kodiic acid, ellagic acid, tranexamic acid and its derivatives, ferulic acid and its derivatives, placenta extract, glutathione, oryzanol, butylresorcinol, oil-soluble chamomile extract, oil-soluble kanzo extract, Nishikawayanagi extract, Plant extracts such as Yukinoshita extract; and the like.
ビタミン類およびその誘導体類としては、例えば、レチノール、酢酸レチノール、パルミチン酸レチノール等のビタミンA類;チアミン塩酸塩、チアミン硫酸塩、リボフラビン、酢酸リボフラビン、塩酸ピリドキシン、ピリドキシンジオクタノエート、ピリドキシンジパルミテート、フラビンアデニンジヌクレオチド、シアノコバラミン、葉酸類、ニコチン酸アミド・ニコチン酸ベンジル等のニコチン酸類、コリン類等のビタミンB群類;アスコルビン酸およびそのナトリウム等の塩等のビタミンC類;ビタミンD;α、β、γ、δ−トコフェロール等のビタミンE類;パントテン酸、ビオチン等のその他ビタミン類;アスコルビン酸リン酸エステルナトリウム塩およびアスコルビン酸リン酸エステルマグネシウム塩等のアスコルビン酸リン酸エステル塩、アスコルビン酸テトライソパルミチン酸エステル・ステアリン酸アスコルビル・パルミチン酸アスコルビル・ジパルミチン酸アスコルビル等のアスコルビン酸脂肪酸エステル、アスコルビン酸エチルエーテル等のアスコルビン酸アルキルエーテル、アスコルビン酸−2−グルコシド等のアスコルビン酸グルコシドおよびその脂肪酸エステル、リン酸トコフェリルアスコルビル等のアスコルビン酸誘導体;ニコチン酸トコフェロール、酢酸トコフェロール、リノール酸トコフェロール、フェルラ酸トコフェロール、トコフェロールリン酸エステル等のトコフェロール誘導体等のビタミン誘導体、トコトリエノール、その他各種ビタミン誘導体類;などが挙げられる。 Examples of vitamins and their derivatives include vitamin As such as retinol, retinol acetate, and retinol palmitate; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxin hydrochloride, pyridoxin dioctanoate, and pyridoxin dipalmi. Vitamin B group such as tate, flavin adenine dinucleotide, cyanocobalamine, folic acid, nicotinic acid such as nicotinic acid amide / benzyl nicotinate, and choline; vitamin C such as ascorbic acid and salts thereof; vitamin D; Vitamin Es such as α, β, γ, δ-tocopherol; Other vitamins such as pantothenic acid and biotinate; Ascorbic acid phosphates such as sodium ascorbic acid phosphate and magnesium ascorbic acid ester, ascorbin Ascorbic acid fatty acid ester such as acid tetraisopalmitic acid ester, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, alkyl ether ascorbic acid such as ethyl ascorbic acid, ascorbic acid glucoside such as ascorbic acid-2-glucoside and the like. Ascorbic acid derivatives such as fatty acid esters and tocopheryl ascorbyl phosphate; vitamin derivatives such as tocopherols such as tocopherol nicotinate, tocopherol acetate, tocopherol linoleate, tocopherol ferrate, tocopherol phosphates, tocotrienol, and various other vitamin derivatives; And so on.
消炎剤および抗炎症剤としては、例えば、グリチルリチン酸およびその誘導体、グリチルレチン酸誘導体、サリチル酸誘導体、ヒノキチオール、グアイアズレン、アラントイン、インドメタシン、酸化亜鉛、酢酸ヒドロコーチゾン、プレドニゾン、塩酸ジフェドラミン、マレイン酸クロルフェニラミン;桃葉エキス、蓬葉エキス等の植物エキス;などが挙げられる。 Examples of anti-inflammatory agents and anti-inflammatory agents include glycyrrhizinic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokithiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, prednisone, diphedramine hydrochloride, chlorpheniramine maleate; Plant extracts such as peach leaf extract and Honoha extract; and the like.
育毛用薬剤、血行促進剤、および刺激剤としては、例えば、センブリエキス、トウガラシチンキ、ショウキョウチンキ、ショウキョウエキス、カンタリスチンキ等の植物エキス・チンキ類;カプサイシン、ノニル酸ワレニルアミド、ジンゲロン、イクタモール、タンニン酸、ボルネオール、シクランデレート、シンナリジン、トラゾリン、アセチルコリン、ベラパミル、セファランチン、γ−オリザノール、セファランチン、ビタミンEおよびニコチン酸トコフェロール・酢酸トコフェロール等の誘導体、γ−オリザノール、ニコチン酸およびニコチン酸アミド・ニコチン酸ベンジルエステル・イノシトールヘキサニコチネート、ニコチンアルコール等の誘導体、アラントイン、感光素301、感光素401、塩化カプロニウム、ペンタデカン酸モノグリセリド、フラバノノール誘導体、スチグマステロールまたはスチグマスタノールおよびその配糖体、ミノキシジルなどが挙げられる。 Examples of hair growth agents, blood circulation promoters, and stimulants include plant extracts and tinctures such as senburi extract, capsicum tincture, ginger tincture, ginger extract, and cantalis tincture; capsaicin, nonyl acid warenylamide, zingerone, and ictamol. , Tannic acid, Borneol, Ciclanderate, Cinnaridine, Trazoline, Acetylcholine, Bellapamil, Cephalanthin, γ-Oryzanol, Cephalantin, Vitamin E and derivatives such as tocopherol nicotinate, tocopherol acetate, γ-Oryzanol, nicotinic acid and nicotinic acid amide. Derivatives such as nicotinic acid benzyl ester inositol hexanicotinate, nicotine alcohol, allantin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, flavanonol derivative, stigmasterol or stigmasterol and its glycoside, minoxidil And so on.
ホルモン類としては、エストラジオール、エストロン、エチニルエストラジオール、コルチゾン、ヒドロコルチゾン、プレドニゾンなどが挙げられる。 Examples of hormones include estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone and the like.
抗しわ剤、抗老化剤、ひきしめ剤、冷感剤、温感剤、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤等のその他の薬効剤としては、例えば、レチノール類、レチノイン酸類、レチノイン酸トコフェリル;乳酸、グリコール酸、グルコン酸、フルーツ酸、サリチル酸およびその配糖体・エステル化物等の誘導体、ヒドロキシカプリン酸、長鎖α−ヒドロキシ脂肪酸、長鎖α−ヒドロキシ脂肪酸コレステリル等のα−またはβ−ヒドロキシ酸類およびその誘導体類;γ−アミノ酪酸、γ−アミノ−β−ヒドロキシ酪酸;カルニチン;クレアチン;セラミド類、スフィンゴシン類;カフェイン、キサンチン等およびその誘導体;コエンザイムQ10、カロチン、リコピン、アスタキサンチン、α−リポ酸等の抗酸化・活性酸素消去剤;カテキン類;ケルセチン等のフラボン類;イソフラボン類;没食子酸およびエステル糖誘導体;タンニン、セサミン、プロトアントシアニジン、クロロゲン酸、リンゴポリフェノール等のポリフェノール類;ルチンおよび配糖体等の誘導体;ヘスペリジンおよび配糖体等の誘導体;リグナン配糖体;グラブリジン、グラブレン、リクイリチン、イソリクイリチン等のカンゾウエキス関連物質;ラクトフェリン;ショウガオール、ジンゲロール;メントール、カンファー、セドロール等の香料物質およびその誘導体;カプサイシン、バニリン等および誘導体;ジエチルトルアミド等の昆虫忌避剤;生理活性物質とシクロデキストリン類との複合体;などが挙げられる。 Other medicinal agents such as anti-wrinkle agents, anti-aging agents, tightening agents, cold sensitizers, warming agents, wound healing promoters, stimulants, painkillers, cell activators, etc. include, for example, retinols, retinoic acids. , Tocopheryl retinoate; derivatives such as lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and its glycosides / esterified products, hydroxycapric acid, long-chain α-hydroxy fatty acid, long-chain α-hydroxy fatty acid cholesteryl, etc. -Or β-hydroxy acids and their derivatives; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; creatin; ceramides, spingosins; caffeine, xanthin and its derivatives; coenzyme Q10, carotene, lycopene Antioxidants and active oxygen scavengers such as astaxanthin and α-lipoic acid; catechins; flavones such as quercetin; isoflavones; gallic acid and ester sugar derivatives; tannins, sesamines, protoanthocyanidins, chlorogenic acids, apple polyphenols, etc. Polyphenols; Derivatives such as rutin and glycosides; Derivatives such as hesperidin and glycosides; Lignan glycosides; Kanzo extract-related substances such as glabridin, glabrene, liquilithin, isoliquiritin; lactoferrin; , Sedrol and other fragrance substances and derivatives thereof; capsaicin, vanillin and the like and derivatives; insect repellents such as diethyl toluamide; complexes of physiologically active substances and cyclodextrins; and the like.
植物・動物・微生物エキスとしては、例えば、アイリスエキス、アシタバエキス、アスナロエキス、アスパラガスエキス、アボガドエキス、アマチャエキス、アーモンドエキス、アルテアエキス、アルニカエキス、アロエエキス、アンズエキス、アンズ核エキス、イチョウエキス、インチコウエキス、ウイキョウエキス、ウコンエキス、ウーロン茶エキス、ウワウルシエキス、エイジツエキス、エチナシ葉エキス、エンメイソウエキス、オウゴンエキス、オウバクエキス、オウレンエキス、オオムギエキス、オタネニンジンエキス、オトギリソウエキス、オドリコソウエキス、オノニスエキス、オランダカラシエキス、オレンジエキス、海水乾燥物、海藻エキス、カキ葉エキス、カキョクエキス、加水分解エラスチン、加水分解コムギ末、加水分解シルク、カッコンエキス、カモミラエキス、油溶性カモミラエキス、カロットエキス、カワラヨモギエキス、カラスムギエキス、カルカデエキス、カンゾウエキス、油溶性カンゾウエキス、キウイエキス、キオウエキス、キクラゲエキス、キナエキス、キューカンバーエキス、キリ葉エキス、グアノシン、グアバエキス、クジンエキス、クチナシエキス、クマザサエキス、クララエキス、クルミエキス、クリエキス、グレープフルーツエキス、クレマティスエキス、黒米エキス、黒砂糖抽出物、黒酢、クロレラエキス、クワエキス、ゲンチアナエキス、ゲンノショウコエキス、紅茶エキス、酵母エキス、コウボクエキス、コーヒーエキス、ゴボウエキス、コメエキス、コメ発酵エキス、コメヌカ発酵エキス、コメ胚芽油、コンフリーエキス、コラーゲン、コケモモエキス、サイシンエキス、サイコエキス、サイタイ抽出液、サフランエキス、サルビアエキス、サボンソウエキス、ササエキス、サンザシエキス、サンシャエキス、サンショウエキス、シイタケエキス、ジオウエキス、シコンエキス、シソエキス、シナノキエキス、シモツケソウエキス、ジャトバエキス、シャクヤクエキス、ショウキュウエキス、ショウブ根エキス、シラカバエキス、白キクラゲエキス、スギナエキス、ステビアエキス、ステビア発酵物、西河柳エキス、セイヨウキズタエキス、セイヨウサンザシエキス、セイヨウニワトコエキス、セイヨウノコギリソウエキス、セイヨウハッカエキス、セージエキス、ゼニアオイエキス、センキュウエキス、センブリエキス、ソウハクヒエキス、ダイオウエキス、ダイズエキス、タイソウエキス、タイムエキス、タンポポエキス、地衣類エキス、茶エキス、チョウジエキス、チガヤエキス、チンピエキス、ティートリー油、甜茶エキス、トウガラシエキス、トウキエキス、トウキンセンカエキス、トウニンエキス、トウヒエキス、ドクダミエキス、トマトエキス、納豆エキス、ニンジンエキス、ニンニクエキス、ノバラエキス、ハイビスカスエキス、バクモンドウエキス、ハスエキス、パセリエキス、バーチエキス、蜂蜜、ハマメリスエキス、パリエタリアエキス、ヒキオコシエキス、ビサボロール、ヒノキエキス、ビフィズス菌エキス、ビワエキス、フキタンポポエキス、フキノトウエキス、ブクリョウエキス、ブッチャーブルームエキス、ブドウエキス、ブドウ種子エキス、プロポリス、ヘチマエキス、ベニバナエキス、ペパーミントエキス、ボダイジュエキス、ボタンエキス、ホップエキス、マイカイカエキス、マツエキス、マロニエエキス、ミズバショウエキス、ムクロジエキス、メリッサエキス、モズクエキス、モモエキス、ヤグルマギクエキス、ユーカリエキス、ユキノシタエキス、ユズエキス、ユリエキス、ヨクイニンエキス、ヨモギエキス、ラベンダーエキス、緑茶エキス、卵殻膜エキス、リンゴエキス、ルイボス茶エキス、レイシエキス、レタスエキス、レモンエキス、レンギョウエキス、レンゲソウエキス、ローズエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス、ワレモコウエキスなどが挙げられる。 Examples of plant / animal / microbial extracts include iris extract, asitaba extract, asunaro extract, asparagus extract, avocado extract, amacha extract, almond extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo biloba. Extract, Inchikou extract, Uikyo extract, Ukon extract, Woolong tea extract, Uwaurushi extract, Agetsu extract, Echinashi leaf extract, Enmeisou extract, Ogon extract, Oubaku extract, Ouren extract, Omugi extract, Otanenjinjin extract, Otogirisou extract, Odorikousou extract, Ononis extract, Dutch mustard extract, orange extract, dried seawater, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, cucumber extract, chamomile extract, oil-soluble chamomile extract, carrot extract, Kawarayomogi extract, crow wheat extract, karukade extract, kanzo extract, oil-soluble kanzo extract, kiwi extract, kiou extract, kikurage extract, kina extract, cucumber extract, kiri leaf extract, guanosine, guaba extract, kuzin extract, kuchinashi extract, kumazasa extract, clara extract, Walnut extract, chestnut extract, grapefruit extract, crematis extract, black rice extract, brown sugar extract, black vinegar, chlorella extract, mulberry extract, gentiana extract, gennoshoco extract, tea extract, yeast extract, koboku extract, coffee extract, gobo extract, rice extract, Fermented rice extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, moss peach extract, saishin extract, psycho extract, saitai extract, saffron extract, salvia extract, sabonsou extract, sasa extract, sanzashi extract, sansha extract, sun Show extract, Shiitake extract, Jio extract, Shikon extract, Shiso extract, Shinanoki extract, Shimotsukesou extract, Jatoba extract, Shakuyaku extract, Shokyu extract, Shobu root extract, Shirakaba extract, White chrysanthemum extract, Sugina extract, Stevia extract, Stevia fermented product, Nishikawayanagi extract , Seiyoukizuta extract, Seiyousanzashi extract, Seiyouniwatoko extract, Seiyounokogirisou extract, Seiyouhakka extract, Sage extract, Zeniaoi extract, Senkyu extract, Senburi extract, Souhakuhi extract, Daiou extract , Soybean extract, Taisou extract, Thyme extract, Dandelion extract, Local clothing extract, Tea extract, Chouji extract, Chigaya extract, Chinpi extract, Tea tree oil, Jincha extract, Togarashi extract, Touki extract, Tokinsenka extract, Tounin extract, Tohi extract, Dokudami extract, Tomato extract, natto extract, carrot extract, garlic extract, Novara extract, hibiscus extract, Bakumondou extract, hass extract, parsley extract, birch extract, honey, hamamelis extract, parietalia extract, hikiokoshi extract, bisaborol, hinoki extract, bifidus extract , Biwa extract, Fukitanpopo extract, Fukinotou extract, Bukuryo extract, Butcher bloom extract, Grape extract, Grape seed extract, Propolis, Hechima extract, Benibana extract, Peppermint extract, Bodaiju extract, Button extract, Hop extract, Maikaika extract, Pine extract, Maronie Extract, Mizubasho extract, Mukuroji extract, Melissa extract, Mozuku extract, Peach extract, Yagurumagiku extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yuri extract, Yokuinin extract, Yomogi extract, Lavender extract, Green tea extract, Eggshell membrane extract, Apple extract, Louis Boss tea Examples thereof include extracts, reishi extract, lettuce extract, lemon extract, lotus extract, lotus extract, rose extract, rosemary extract, roman chamomile extract, royal jelly extract, and crackle extract.
鎮痒剤としては、例えば、塩酸ジフェンヒドラミン、マレイン酸クロルフェニラミン、カンファー、サブスタンス−P阻害剤などが挙げられる。 Examples of the antipruritic agent include diphenhydramine hydrochloride, chlorpheniramine maleate, camphor, substance-P inhibitor and the like.
角質剥離・溶解剤としては、例えば、サリチル酸、イオウ、レゾルシン、硫化セレン、ピリドキシンなどが挙げられる。 Examples of the exfoliating / dissolving agent include salicylic acid, sulfur, resorcin, selenium sulfide, and pyridoxine.
制汗剤としては、例えば、クロルヒドロキシアルミニウム、塩化アルミニウム、酸化亜鉛、パラフェノールスルホン酸亜鉛などが挙げられる。 Examples of the antiperspirant include chlorohydroxyaluminum, aluminum chloride, zinc oxide, zinc paraphenol sulfonate and the like.
清涼剤としては、例えば、メントール、サリチル酸メチルが挙げられる。 Examples of the refreshing agent include menthol and methyl salicylate.
収れん剤としては、例えば、クエン酸、酒石酸、乳酸、硫酸アルミニウム・カリウム、タンニン酸などが挙げられる。 Examples of the astringent include citric acid, tartaric acid, lactic acid, aluminum / potassium sulfate, and tannic acid.
酵素としては、例えば、スーパーオキサイドディスムターゼ、カタラーゼ、塩化リゾチーム、リパーゼ、パパイン、パンクレアチン、プロテアーゼなどが挙げられる。 Examples of the enzyme include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease and the like.
核酸としては、例えば、リボ核酸およびその塩、デオキシリボ核酸およびその塩、アデノシン三リン酸二ナトリウムなどが挙げられる。 Examples of the nucleic acid include ribonucleic acid and a salt thereof, deoxyribonucleic acid and a salt thereof, disodium adenosine triphosphate and the like.
香料としては、例えば、アセチルセドレン、アミルシンナムアルデヒド、アリルアミルグリコレート、β−イオノン、イソイースーパー、イソブチルキノリン、イリス油、イロン、インドール、イランイラン油、ウンデカナール、ウンデセナール、γ−ウンデカラクトン、エストラゴール、オイゲノール、オークモス、オポポナックスレジノイド、オレンジ油、オイゲノール、オーランチオール、ガラクソリッド、カルバクロール、L−カルボン、カンファー、キャノン、キャロットシード油、クローブ油、ケイヒ酸メチル、ゲラニオール、ゲラニルニトリル、酢酸イソボルニル、酢酸ゲラニル、酢酸ジメチルベンジルカルビニル、酢酸スチラリル、酢酸セドリル、酢酸テレピネル、酢酸p−t−ブチルシクロヘキシル、酢酸ベチベリル、酢酸ベンジル、酢酸リナリル、サリチル酸イソペンチル、サリチル酸ベンジル、サンダルウッド油、サンタロール、シクラメンアルデヒド、シクロペンタデカノリド、ジヒドロジャスモン酸メチル、ジヒドロミルセノール、ジャスミンアブソリュート、ジャスミンラクトン、cis−ジャスモン、シトラール、シトロネノール、シトロネラール、シナモンバーク油、1,8−シネオール、シンナムアルデヒド、スチラックスレジノイド、セダーウッド油、セドレン、セドロール、セロリシード油、タイム油、ダマスコン、ダマセノン、チモール、チュベローズアブソリュート、デカナール、デカラクトン、テルピネオール、γ−テルピネン、トリプラール、ネロール、ノナナール、2,6−ノナジエノール、ノナラクトン、パチョリアルコール、バニラアブソリュート、バニリン、バジル油、パチョリ油、ヒドロキシシトロネラール、α−ピネン、ピペリトン、フェネチルアルコール、フェニルアセトアルデヒド、プチグレン油、ヘキシルシンナムアルデヒド、cis−3−ヘキセノール、ペルーバルサム、ベチバー油、ベチベロール、ペパーミント油、ペパー油、ヘリオトロピン、ベルガモット油、ベンジルベンゾエート、ボルネオール、ミルレジノイド、ムスクケトン、メチルノニルアセトアルデヒド、γ−メチルヨノン、メントール、L−メントール、L−メントン、ユーカリ油、β−ヨノン、ライム油、ラベンダー油、D−リモネン、リナロール、リラール、リリアール、レモン油、ローズアブソリュート、ローズオキシド、ローズ油、ローズマリー油、各種精油等の合成香料および天然香料並びに各種調合香料などが挙げられる。 Examples of fragrances include acetylsedrene, amylcinnamaldehyde, allylamylglycolate, β-ionone, isoe super, isobutylquinolin, iris oil, iron, indole, ylang ylang oil, undecanal, undecenal, and γ-undeca. Lactone, estragor, eugenol, oak moss, opoponax resinoid, orange oil, eugenol, aulanthiol, galactorsolid, carbacrol, L-carboxylic, camphor, cannon, carrot seed oil, clove oil, methyl silicate, geraniol, Geranylnitrile, isobornyl acetate, geranyl acetate, dimethylbenzyl carvinyl acetate, styralyl acetate, sedrill acetate, telepinel acetate, pt-butylcyclohexyl acetate, vetiveryl acetate, benzyl acetate, linalyl acetate, isopentyl salicylate, benzyl salicylate, sandalwood oil , Santalol, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromilsenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, citroneral, cinnamon bark oil, 1,8-cineole, cinna Mualdehyde, stylux resinoid, cedarwood oil, sedrene, sedrol, celery seed oil, thyme oil, damascon, damasenon, timol, tuberose absolute, decanal, decalactone, terpineol, γ-terpinen, triplar, nerol, nonanaal, 2,6-nonadienol , Nonalactone, Pacholi alcohol, Vanilla absolute, Vanillin, Basil oil, Pachori oil, Hydroxycitroneral, α-pinene, Piperiton, Phenethyl alcohol, Phenylacetaldehyde, Petitgrain oil, Hexylcinnamaldehyde, cis-3-hexenol, Peruval balsam, Vetiber oil, vetiberol, peppermint oil, pepper oil, heliotropin, bergamot oil, benzylbenzoate, borneol, milresinoid, muskketone, methylnonylacetaldehyde, γ-methylyonone, menthol, L-menthol, L-menton, eucalyptus oil, β- Synthetic fragrances such as ionone, lime oil, lavender oil, D-limonen, linalol, linal, lilial, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, and various essential oils. And natural fragrances and various blended fragrances.
色素、着色剤、染料、および顔料としては、例えば、褐色201号、黒色401号、紫色201号、紫色401号、青色1号、青色2号、青色201号、青色202号、青色203号、青色204号、青色205号、青色403号、青色404号、緑色201号、緑色202号、緑色204号、緑色205号、緑色3号、緑色401号、緑色402号、赤色102号、赤色104−1号、赤色105−1号、赤色106号、赤色2号、赤色201号、赤色202号、赤色203号、赤色204号、赤色205号、赤色206号、赤色207号、赤色208号、赤色213号、赤色214号、赤色215号、赤色218号、赤色219号、赤色220号、赤色221号、赤色223号、赤色225号、赤色226号、赤色227号、赤色228号、赤色230−1号、赤色230−2号、赤色231号、赤色232号、赤色3号、赤色401号、赤色404号、赤色405号、赤色501号、赤色502号、赤色503号、赤色504号、赤色505号、赤色506号、橙色201号、橙色203号、橙色204号、橙色205号、橙色206号、橙色207号、橙色401号、橙色402号、橙色403号、黄色201号、黄色202−1号、黄色202−2号、黄色203号、黄色204号、黄色205号、黄色4号、黄色401号、黄色402号、黄色403−1号、黄色404号、黄色405号、黄色406号、黄色407号、黄色5号等の法定色素;Acid Red 14等のその他酸性染料;Arianor Sienna Brown、Arianor Madder Red、Arianor Steel Blue、Arianor Straw Yellow等の塩基染料;HC Yellow 2、HC Yellow 5、HC Red 3、4−hydoxypropylamino−3−nitrophenol、N,N’bis(2−hydroxyethyl)−2−nitro−p−phenylenediamine、HC Blue 2、Basic Blue 26等のニトロ染料;分散染料;二酸化チタン、酸化亜鉛等の無機白色顔料;酸化鉄(ベンガラ)、チタン酸鉄等の無機赤色系顔料;γ−酸化鉄等の無機褐色系顔料;黄酸化鉄、黄土等の無機黄色系顔料;黒酸化鉄、低次酸化チタン等の無機黒色系顔料;マンゴバイオレット、コバルトバイオレット等の無機紫色系顔料;酸化クロム、水酸化クロム、チタン酸コバルト等の無機緑色系顔料;群青、紺青等の無機青色系顔料;酸化チタンコーテッドマイカ、酸化チタンコーテッドオキシ塩化ビスマス、酸化チタンコーテッドタルク、着色酸化チタンコーテッドマイカ、オキシ塩化ビスマス、魚鱗箔等のパール顔料;アルミニウムパウダー、カッパーパウダー、金等の金属粉末顔料;表面処理無機および金属粉末顔料;赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色228号、赤色405号、橙色203号、橙色204号、黄色205号、黄色401号、青色404号、赤色3号、赤色104号、赤色106号、赤色227号、赤色230号、赤色401号、赤色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、緑色3号、青色1号等のジルコニウム、バリウムまたはアルミニウムレーキ等の有機顔料;表面処理有機顔料;アスタキサンチン、アリザリン等のアントラキノン類、アントシアニジン、β−カロチン、カテナール、カプサンチン、カルコン、カルサミン、クエルセチン、クロシン、クロロフィル、クルクミン、コチニール、シコニン等のナフトキノン類、ビキシン、フラボン類、ベタシアニジン、ヘナ、ヘモグロビン、リコピン、リボフラビン、ルチン等の天然色素・染料;p−フェニレンジアミン、トルエン−2,5−ジアミン、o−,m−,若しくはp−アミノフェノール、m−フェニレンジアミン、5−アミノ−2−メチルフェノール、レゾルシン、1−ナフトール、2,6−ジアミノピリジン等およびその塩等の酸化染料中間体およびカップラー;インドリン等の自動酸化型染料;ジヒドロキシアセトン;などが挙げられる。 Examples of dyes, colorants, dyes, and pigments include brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, and blue 203. Blue 204, Blue 205, Blue 403, Blue 404, Green 201, Green 202, Green 204, Green 205, Green 3, Green 401, Green 402, Red 102, Red 104 -1, Red 105-1, Red 106, Red 2, Red 201, Red 202, Red 203, Red 204, Red 205, Red 206, Red 207, Red 208, Red 213, Red 214, Red 215, Red 218, Red 219, Red 220, Red 221 and Red 223, Red 225, Red 226, Red 227, Red 228, Red 230 -1, Red 230-2, Red 231, Red 232, Red 3, Red 401, Red 404, Red 405, Red 501, Red 502, Red 503, Red 504, Red No. 505, Red No. 506, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Yellow No. 201, Yellow No. 202 -1, Yellow 202-2, Yellow 203, Yellow 204, Yellow 205, Yellow 4, Yellow 401, Yellow 402, Yellow 403-1, Yellow 404, Yellow 405, Yellow 406 Legal dyes such as No., Yellow No. 407, Yellow No. 5; Other acidic dyes such as Acid Red 14; Basic dyes such as Arianor Sienna Brown, Arianor Madder Red, Arianor Steel Blue, Arianor Straw Yellow; HC Yellow 2, HC Yell , HC Red 3, 4-hydoxypropylamino-3-nitrophenol, N, N'bis (2-yellowzyl) -2-nitro-p-phenylenediamine, HC Blue 2, Basic Blue 26 and other nitro dyes; disperse dyes, titanium dioxide, Inorganic white pigments such as zinc oxide; inorganic red pigments such as iron oxide (Bengala) and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and ocher; black iron oxide , Inorganic black pigments such as low-order titanium oxide; Mango Violet, Inorganic purple pigments such as cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate; inorganic blue pigments such as ultramarine and dark blue; titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide Pearl pigments such as coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil; metal powder pigments such as aluminum powder, copper powder, gold; surface-treated inorganic and metal powder pigments; red 201, red 202, red No. 204, No. 205, No. 220, No. 220, No. 226, No. 228, No. 405, No. 203, No. 204, Yellow No. 205, No. 401, No. 404, No. 3, Red No. 104 , Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc. Organic pigments such as zirconium, barium or aluminum lake; Surface-treated organic pigments; anthracinones such as astaxanthin and alizarin, anthocyanidins, β-carotene, catenal, capsantin, chalcone, calsamine, quercetin, crosin, chlorophyll, curcumin, cochineal, ciconin and the like. Natural pigments and dyes such as naphthoquinones, bixins, flavones, betacyanidine, henna, hemoglobin, lycopene, riboflavin, rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m-, or p- Oxidation dye intermediates and couplers such as aminophenol, m-phenylenediamine, 5-amino-2-methylphenol, resorcin, 1-naphthol, 2,6-diaminopyridine and salts thereof; automatic oxidation dyes such as indolin; Dihydroxyacetone; and the like.
本発明の保湿剤、皮膚化粧料、皮膚外用剤、または頭髪化粧料には、これらの添加成分の他、化粧品原料基準、化粧品種別配合成分規格、日本化粧品工業連合会成分表示名称リスト、INCI辞書(The International Cosmetic Ingredient Dictionary and Handbook)、医薬部外品原料規格、日本薬局方、医薬品添加物規格、食品添加物公定書等に記載されている成分、および、国際特許分類IPCがA61K7の分類に属する日本国および諸外国特許公報および特許公開公報(公表公報・再公表を含む)に記載されている成分等、公知の化粧料成分、医薬品成分、食品成分などを、公知の組み合わせおよび配合比・配合量で含有させることが可能である。 In addition to these additive ingredients, the moisturizer, skin cosmetics, skin external preparations, or hair cosmetics of the present invention include cosmetic raw material standards, compounding ingredient standards for each cosmetic type, Japanese Cosmetic Industry Association ingredient display name list, INCI dictionary. (The International Cosmetic Ingredient Dictionary and Handbook), Ingredients listed in Pharmaceutical Ingredients Standards, Japanese Pharmacy, Pharmaceutical Additives Standards, Food Additives Official Standards, etc., and International Patent Classification IPC is classified as A61K7 Known combinations and compounding ratios of known cosmetic ingredients, pharmaceutical ingredients, food ingredients, etc., such as ingredients described in Japanese and foreign patent gazettes and patent publication gazettes (including published gazettes and republished gazettes) to which they belong. It can be contained in a blending amount.
本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料は、本発明の効果を損なわない範囲で、任意の適切な方法によって製造し得る。 The skin cosmetics, external preparations for skin, or hair cosmetics of the present invention can be produced by any suitable method as long as the effects of the present invention are not impaired.
本発明の皮膚化粧料、皮膚外用剤、または頭髪化粧料の剤型としては、例えば、水中油(O/W)型、油中水(W/O)型、W/O/W型、O/W/O型等の乳化型化粧料、油性化粧料、固形化粧料、液状化粧料、練状化粧料、スティック状化粧料、揮発性油型化粧料、粉状化粧料、ゼリー状化粧料、ジェル状化粧料、ペースト状化粧料、乳化高分子型化粧料、シート状化粧料、ミスト状化粧料、スプレー型化粧料等の剤型などが挙げられる。 Examples of the skin cosmetics, external skin preparations, or hair cosmetics of the present invention include oil-in-water (O / W) type, water-in-oil (W / O) type, W / O / W type, and O. / W / O type emulsified cosmetics, oily cosmetics, solid cosmetics, liquid cosmetics, paste cosmetics, stick cosmetics, volatile oil cosmetics, powder cosmetics, jelly cosmetics , Gel-like cosmetics, paste-like cosmetics, emulsified polymer-type cosmetics, sheet-like cosmetics, mist-like cosmetics, spray-type cosmetics and the like.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「%」は「質量%」を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
<ゲルパーミエーションクロマトグラフィー(GPC)>
ポリマーの重量平均分子量(Mw)は、GPC(ゲルパーミエーションクロマトグラフィー)により測定した。測定条件、装置などは以下の通りである。
装置:東ソー社製 EcoSEC HLC−8320GPC
検出器:示差屈折率計(RI)検出器
カラム:SHODEX製 Asahipak GF−1G−7B、GF−310−HQ、GF−710−HQ
カラム温度:40℃
流速:0.5mL/min
注入量:10μL(試料濃度0.4wt%の溶離液調製溶液)
検量線:ジーエルサイエンス社製 ポリエチレングリコール
GPCソフト:東ソー社製 EcoSEC−WS
溶離液:0.1M酢酸ナトリウム/アセトニトリル=70/30(v/v)
<Gel Permeation Chromatography (GPC)>
The weight average molecular weight (Mw) of the polymer was measured by GPC (gel permeation chromatography). The measurement conditions, equipment, etc. are as follows.
Equipment: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector Column: SHODEX Asahipak GF-1G-7B, GF-310-HQ, GF-710-HQ
Column temperature: 40 ° C
Flow velocity: 0.5 mL / min
Injection volume: 10 μL (sample concentration 0.4 wt% eluent preparation solution)
Calibration curve: Polyethylene glycol GPC software manufactured by GL Sciences: EcoSEC-WS manufactured by Tosoh Corporation
Eluent: 0.1M sodium acetate / acetonitrile = 70/30 (v / v)
<単量体の分析>
単量体の分析は、以下の条件で、液体クロマトグラフィーを用いて測定した。
装置:資生堂「NANOSPACESI−2」
カラム:資生堂「CAPCELLPAK C18 UG120」
カラム温度:20℃
流速;0.1ml/min
溶離液:LC用メタノール(和光純薬工業株式会社製)/超純水=1/24(質量比)、1−ヘプタンスルホン酸ナトリウム0.4質量%添加
<Analysis of monomer>
The analysis of the monomer was measured using liquid chromatography under the following conditions.
Equipment: Shiseido "NANOSPACESI-2"
Column: Shiseido "CAPCELLPAK C18 UG120"
Column temperature: 20 ° C
Flow velocity; 0.1 ml / min
Eluent: Methanol for LC (manufactured by Wako Pure Chemical Industries, Ltd.) / Ultrapure water = 1/24 (mass ratio), 0.4% by mass of sodium 1-heptane sulfonate added
<塗布感触(弾力感)の評価>
評価者3名で、塗布感触(弾力感)を評価した。
5mL点眼瓶に入れたサンプル溶液を前腕内側に1滴滴下して人差し指で塗り込み、サンプル溶液を塗布し肌に塗り広げる際(水溶液状態)に感じる塗布感触(弾力感)(膜厚感)を評価した。弾力感は、肌に塗布して塗り込む際の指の左右の動きに対して上向きにはたらく力(法線応力)であり、表現としては膜厚感ともいう。弾力感は存在するほうが好ましい。評価は11段階で、数字が大きい方が強く、評価者3名での話し合いで決定した。
主な保湿剤の評価は以下のとおりである。
10点:高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)0.5%水溶液
3点:純水、グリセリン27%水溶液、スクロース30%水溶液
<Evaluation of application feel (elasticity)>
Three evaluators evaluated the feeling of application (feeling of elasticity).
Drop one drop of the sample solution in a 5 mL eye drop bottle on the inside of the forearm, apply it with your index finger, apply the sample solution and spread it on the skin (aqueous solution state) to feel the application feel (elasticity) (film thickness) evaluated. The feeling of elasticity is the force (normal stress) that acts upward with respect to the left and right movement of the finger when it is applied to the skin, and is also called the feeling of film thickness as an expression. It is preferable that a feeling of elasticity exists. The evaluation was made in 11 stages, and the larger the number, the stronger it was, and it was decided through discussions with three evaluators.
The evaluation of the main moisturizers is as follows.
10 points: High molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") 0.5% aqueous solution 3 points: pure water, glycerin 27% aqueous solution, sucrose 30% aqueous solution
<残存感触(摩擦感・粘着感)の評価>
評価者3名で、塗布感触(摩擦感・粘着感)を評価した。
5mL点眼瓶に入れたサンプル溶液を前腕内側に1滴滴下して人差し指で塗り込み、完全に塗布し終えた際(水分蒸発状態)に、溶液を塗布し終えた面を指で触った時に感じる「摩擦感」(きしみや、すべすべ感)、「粘着感」(べたつきやしっとり感)を評価した。摩擦感は、指の左右の動きに対して逆向きにはたらく力(動的摩擦力)であり、摩擦感がない場合はすべすべ感になり、好ましい。粘着感は、指を肌から引き離す上向きの力に対して下向きにはたらく力(引きはがし抵抗力)であり、べたべた、もちもち、しっとり等と表現される。一般に、粘着感が強い場合は不快なべたつき、弱く適度にある場合は良好なしっとり感を示す。評価は10段階で、数値が大きい方が強く、評価者3名での話し合いで決定した。
主な保湿剤の評価は以下のとおりである。
10点:スクロース30%水溶液
8点:スクロース16%水溶液
4点:グリセリン27%水溶液
3点:純水(何も塗布しない)
残存感触の粘着感評価の数値について、1〜4は粘着感が弱すぎる範囲であり、5〜7は粘着感が弱く適度にある範囲で好ましく、8〜10は粘着感が強く不快なべたつきとされる範囲である。残存感触の粘着感の評価で好ましい粘着性をもつとされたサンプル(粘着感5〜7に相当する)についてのみ、残存感触の摩擦感の評価を行った。
<Evaluation of residual feel (friction / adhesive)>
Three evaluators evaluated the coating feel (friction / adhesion).
Drop one drop of the sample solution in a 5 mL eye drop bottle on the inside of the forearm, apply it with your index finger, and when you have completely applied it (water evaporation state), you will feel it when you touch the surface to which the solution has been applied. "Friction" (squeaky and smooth feeling) and "adhesiveness" (sticky and moist feeling) were evaluated. The frictional feeling is a force (dynamic frictional force) that acts in the opposite direction to the left and right movement of the finger, and when there is no frictional feeling, it becomes a smooth feeling, which is preferable. The sticky feeling is a force that acts downward against an upward force that pulls a finger away from the skin (peeling resistance), and is expressed as sticky, sticky, moist, or the like. Generally, when the stickiness is strong, it shows an unpleasant stickiness, and when it is weak and moderate, it shows a good moist feeling. The evaluation was made on a scale of 10, with the larger the value being stronger, and the decision was made through discussions among the three evaluators.
The evaluation of the main moisturizers is as follows.
10 points: 30% aqueous solution of sucrose 8 points: 16% aqueous solution of sucrose 4 points: 27% aqueous solution of glycerin 3 points: pure water (no application is applied)
Regarding the numerical value of the adhesiveness evaluation of the residual feel, 1 to 4 are in the range where the adhesiveness is too weak, 5 to 7 are preferable in the range where the adhesiveness is weak and moderate, and 8 to 10 are strong and unpleasant stickiness. It is the range to be done. The frictional feeling of the residual feeling was evaluated only for the samples (corresponding to the adhesive feelings 5 to 7) having a preferable adhesiveness in the evaluation of the adhesive feeling of the residual feeling.
<保湿性の評価>
保湿性は、以下の条件で、被験者の角層水分量をSKICON−200EXを用いてコンダクタンスを測定することで評価した。
装置:SKICON−200EX(IBS社製)
測定環境:温度25℃、湿度30%
被験者の前腕内側を洗浄し余分な汚れや皮脂を除去した。15分後に、50μLのサンプル溶液を8cm2に塗布した。5分後に、塗膜の上からSKICON−200EXを用いてコンダクタンスを測定した。さらに1時間後と2時間後に50μLのサンプル溶液を8cm2に再塗布し、3時間後に塗膜の上から再度コンダクタンスを測定した。
<Evaluation of moisturizing property>
The moisturizing property was evaluated by measuring the conductance of the subject's stratum corneum water content using SKICON-200EX under the following conditions.
Equipment: SKICON-200EX (manufactured by IBS)
Measurement environment: temperature 25 ° C, humidity 30%
The inside of the subject's forearm was washed to remove excess dirt and sebum. After 15 minutes, 50 μL of sample solution was applied to 8 cm 2 . After 5 minutes, the conductance was measured from above the coating film using SKICON-200EX. After 1 hour and 2 hours, 50 μL of the sample solution was reapplied to 8 cm 2, and after 3 hours, the conductance was measured again from above the coating film.
〔合成例1〕(NVP/SA=80/20の共重合体(1)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水136.0gを仕込み、撹拌下、80℃に昇温した。次いで、撹拌下、80℃一定状態の重合反応系中に、N−ビニルピロリドン(以下、NVPと略す)51.2g、アクリル酸ナトリウム(以下、SAと略す)の20%水溶液64.0g、ジメチル2,2’−アゾビス(2−メチルプロピオンアミジン)二塩酸塩(以下、V−50と略す)の10%水溶液6.4gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、NVPとV−50の10%水溶液は120分間連続的に滴下した。SAの20%水溶液は60.8gを120分間で滴下したのち、残りを30分間で滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で60分間保持したのち、重合反応を完結させ、共重合体(1)を得た。得られた共重合体(1)の重量平均分子量は120,000であった。
[Synthesis Example 1] (Synthesis of copolymer (1) of NVP / SA = 80/20)
136.0 g of pure water was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Next, under stirring, 51.2 g of N-vinylpyrrolidone (hereinafter abbreviated as NVP), 64.0 g of a 20% aqueous solution of sodium acrylate (hereinafter abbreviated as SA), and dimethyl were placed in a polymerization reaction system at a constant state of 80 ° C. 6.4 g of a 10% aqueous solution of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (hereinafter abbreviated as V-50) was added dropwise from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the 10% aqueous solution of NVP and V-50 was continuously dropped for 120 minutes. 60.8 g of a 20% aqueous solution of SA was added dropwise over 120 minutes, and the rest was added dropwise over 30 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 60 minutes, and then the polymerization reaction was completed to obtain a copolymer (1). The weight average molecular weight of the obtained copolymer (1) was 120,000.
〔合成例2〕(NVP/SA=80/20の共重合体(2)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水136.0gを仕込み、撹拌下、80℃に昇温した。次いで、撹拌下、80℃一定状態の重合反応系中に、NVP51.2g、SAの20%水溶液64.0g、V−50の10%水溶液3.2gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、NVPとV−50の10%水溶液は120分間連続的に滴下した。SAの20%水溶液は60.8gを120分間で滴下したのち、残りを30分間で滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で60分間保持したのち、重合反応を完結させ、共重合体(2)を得た。得られた共重合体(2)の重量平均分子量は200,000であった。
[Synthesis Example 2] (Synthesis of copolymer (2) of NVP / SA = 80/20)
136.0 g of pure water was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Then, under stirring, 51.2 g of NVP, 64.0 g of a 20% aqueous solution of SA, and 3.2 g of a 10% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the 10% aqueous solution of NVP and V-50 was continuously dropped for 120 minutes. 60.8 g of a 20% aqueous solution of SA was added dropwise over 120 minutes, and the rest was added dropwise over 30 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 60 minutes, and then the polymerization reaction was completed to obtain a copolymer (2). The weight average molecular weight of the obtained copolymer (2) was 200,000.
〔合成例3〕(NVP/SA=95/5の共重合体(3)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水175.9gを仕込み、撹拌下、80℃に昇温した。次いで、撹拌下、80℃一定状態の重合反応系中に、NVP60.8g、SAの20%水溶液16.0g、V−50の10%水溶液3.2gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、NVPとV−50の10%水溶液は120分間連続的に滴下した。SAの20%水溶液は15.2gを120分間で滴下したのち、残りを30分間で滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で60分間保持したのち、重合反応を完結させ、共重合体(3)を得た。得られた共重合体(3)の重量平均分子量は190,000であった。
[Synthesis Example 3] (Synthesis of copolymer (3) of NVP / SA = 95/5)
175.9 g of pure water was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Then, under stirring, 60.8 g of NVP, 16.0 g of a 20% aqueous solution of SA, and 3.2 g of a 10% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the 10% aqueous solution of NVP and V-50 was continuously dropped for 120 minutes. 15.2 g of a 20% aqueous solution of SA was added dropwise over 120 minutes, and the rest was added dropwise over 30 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 60 minutes, and then the polymerization reaction was completed to obtain a copolymer (3). The weight average molecular weight of the obtained copolymer (3) was 190,000.
〔合成例4〕(NVP/HEA=80/20の共重合体(4)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水144.3gを仕込み、撹拌下、80℃に昇温した。次いで、単量体溶液(1)として、ヒドロキシエチルアクリレート12.8gに純水32.0gを加え、ジエタノールアミンでpH8〜9にした溶液を調製した。撹拌下、80℃一定状態の重合反応系中に、NVP51.2g、単量体溶液(1)44.8g、V−50の1%水溶液16.0gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、120分間連続的に滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で30分間保持したのち、重合反応を完結させ、共重合体(4)を得た。得られた共重合体(4)の重量平均分子量は200,000であった。
[Synthesis Example 4] (Synthesis of copolymer (4) of NVP / HEA = 80/20)
144.3 g of pure water was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Next, as a monomer solution (1), 32.0 g of pure water was added to 12.8 g of hydroxyethyl acrylate to prepare a solution having a pH of 8 to 9 with diethanolamine. Under stirring, 51.2 g of NVP, 44.8 g of the monomer solution (1), and 16.0 g of a 1% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the dropping was continued for 120 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 30 minutes, and then the polymerization reaction was completed to obtain a copolymer (4). The weight average molecular weight of the obtained copolymer (4) was 200,000.
〔合成例5〕(NVP/HEMA=80/20の共重合体(5)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水144.3gを仕込み、撹拌下、80℃に昇温した。次いで、単量体溶液(1)として、ヒドロキシエチルメタクリレート12.8gに純水32.0gを加え、ジエタノールアミンでpH8〜9にした溶液を調製した。撹拌下、80℃一定状態の重合反応系中に、NVP51.2g、単量体溶液(1)44.8g、V−50の1%水溶液16.0gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、120分間連続的に滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で30分間保持したのち、重合反応を完結させ、共重合体(5)を得た。得られた共重合体(5)の重量平均分子量は222,000であった。
[Synthesis Example 5] (Synthesis of copolymer (5) of NVP / HEMA = 80/20)
144.3 g of pure water was charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Next, as a monomer solution (1), 32.0 g of pure water was added to 12.8 g of hydroxyethyl methacrylate to prepare a solution having a pH of 8 to 9 with diethanolamine. Under stirring, 51.2 g of NVP, 44.8 g of the monomer solution (1), and 16.0 g of a 1% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the dropping was continued for 120 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 30 minutes, and then the polymerization reaction was completed to obtain a copolymer (5). The weight average molecular weight of the obtained copolymer (5) was 222,000.
〔合成例6〕(NVP/メタクリル酸PEGエステル=50/50の共重合体(6)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水143.0gを仕込み、撹拌下、80℃に昇温した。次いで、単量体溶液(2)として、メタクリル酸のメトキシポリエチレングリコールエステル(EO鎖長=9モル)32.0gに純水32.0gを加え、ジエタノールアミンでpH8〜9にした溶液を調製した。撹拌下、80℃一定状態の重合反応系中に、NVP32.0g、単量体溶液(2)64.0g、V−50の1%水溶液14.7gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、120分間連続的に滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で30分間保持したのち、重合反応を完結させ、共重合体(6)を得た。得られた共重合体(6)の重量平均分子量は188,000であった。
[Synthesis Example 6] (Synthesis of NVP / Methacrylic Acid PEG Ester = 50/50 Copolymer (6))
143.0 g of pure water was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Next, as a monomer solution (2), 32.0 g of pure water was added to 32.0 g of methoxypolyethylene glycol ester of methacrylic acid (EO chain length = 9 mol) to prepare a solution having a pH of 8 to 9 with diethanolamine. Under stirring, 32.0 g of NVP, 64.0 g of the monomer solution (2), and 14.7 g of a 1% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the dropping was continued for 120 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 30 minutes, and then the polymerization reaction was completed to obtain a copolymer (6). The weight average molecular weight of the obtained copolymer (6) was 188,000.
〔比較合成例1〕(NVP/SA=80/20の比較共重合体(1)の合成)
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水128.0gを仕込み、撹拌下、80℃に昇温した。次いで、撹拌下、80℃一定状態の重合反応系中に、NVP51.2g、SAの20%水溶液64.0g、V−50の10%水溶液16.0gを、それぞれ別々の滴下ノズルより滴下した。滴下時間に関して、全て同時に滴下を開始し、NVPとV−50の10%水溶液は120分間連続的に滴下した。SAの20%水溶液は60.8gを120分間で滴下したのち、残りを30分間で滴下した。滴下完了後から30分後にV−50の10%水溶液0.6gを加え、さらに80℃で60分間保持したのち、重合反応を完結させ、比較共重合体(1)を得た。得られた比較共重合体(1)の重量平均分子量は51,000であった。
[Comparative Synthesis Example 1] (Synthesis of Comparative Copolymer (1) with NVP / SA = 80/20)
128.0 g of pure water was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 80 ° C. under stirring. Then, under stirring, 51.2 g of NVP, 64.0 g of a 20% aqueous solution of SA, and 16.0 g of a 10% aqueous solution of V-50 were added dropwise to the polymerization reaction system at a constant state of 80 ° C. from separate dropping nozzles. With respect to the dropping time, dropping was started at the same time, and the 10% aqueous solution of NVP and V-50 was continuously dropped for 120 minutes. 60.8 g of a 20% aqueous solution of SA was added dropwise over 120 minutes, and the rest was added dropwise over 30 minutes. Thirty minutes after the completion of the dropping, 0.6 g of a 10% aqueous solution of V-50 was added, and the mixture was further held at 80 ° C. for 60 minutes, and then the polymerization reaction was completed to obtain a comparative copolymer (1). The weight average molecular weight of the obtained comparative copolymer (1) was 51,000.
〔実施例1−1〕
合成例1で得られた共重合体(1)を1質量%含む水溶液を調整し、評価を行った。結果を表1に示した。
[Example 1-1]
An aqueous solution containing 1% by mass of the copolymer (1) obtained in Synthesis Example 1 was prepared and evaluated. The results are shown in Table 1.
〔実施例1−2〕
合成例2で得られた共重合体(2)を1質量%含む水溶液を調整し、評価を行った。結果を表1に示した。
[Example 1-2]
An aqueous solution containing 1% by mass of the copolymer (2) obtained in Synthesis Example 2 was prepared and evaluated. The results are shown in Table 1.
〔比較例1−1〕
比較合成例1で得られた比較共重合体(1)を1質量%含む水溶液を調整し、評価を行った。結果を表1に示した。
[Comparative Example 1-1]
An aqueous solution containing 1% by mass of the comparative copolymer (1) obtained in Comparative Synthesis Example 1 was prepared and evaluated. The results are shown in Table 1.
〔比較例1−2〕
高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.3質量%含む水溶液を調整し、評価を行った。結果を表1に示した。
[Comparative Example 1-2]
An aqueous solution containing 0.3% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. The results are shown in Table 1.
〔比較例1−3〕
グリセリン(富士フィルム和光純薬工業、試薬)を10質量%含む水溶液を調整し、評価を行った。結果を表1に示した。
[Comparative Example 1-3]
An aqueous solution containing 10% by mass of glycerin (Fujifilm Wako Pure Chemical Industries, Ltd., reagent) was prepared and evaluated. The results are shown in Table 1.
〔実施例2−1〕
合成例1で得られた共重合体(1)を3質量%、高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%含む水溶液を調整し、評価を行った。結果を表2に示した。
[Example 2-1]
An aqueous solution containing 3% by mass of the copolymer (1) obtained in Synthesis Example 1 and 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. .. The results are shown in Table 2.
〔実施例2−2〕
合成例2で得られた共重合体(2)を3質量%、高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%含む水溶液を調整し、評価を行った。結果を表2に示した。
[Example 2-2]
An aqueous solution containing 3% by mass of the copolymer (2) obtained in Synthesis Example 2 and 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. .. The results are shown in Table 2.
〔比較例2−1〕
比較合成例1で得られた比較共重合体(1)を3質量%、高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%含む水溶液を調整し、評価を行った。結果を表2に示した。
[Comparative Example 2-1]
An aqueous solution containing 3% by mass of the comparative copolymer (1) obtained in Comparative Synthesis Example 1 and 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. went. The results are shown in Table 2.
〔比較例2−2〕
高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.3質量%含む水溶液を調整し、評価を行った。結果を表2に示した。
[Comparative Example 2-2]
An aqueous solution containing 0.3% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. The results are shown in Table 2.
〔比較例2−3〕
高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%含む水溶液を調整し、評価を行った。結果を表2に示した。
[Comparative Example 2-3]
An aqueous solution containing 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") was prepared and evaluated. The results are shown in Table 2.
実施例2−1、実施例2−2は残存感触の粘着感が適度にありながら、摩擦感も低減しており、使用感に優れることがわかる。 It can be seen that in Examples 2-1 and 2-2, the feeling of stickiness of the residual feel is moderate, but the feeling of friction is also reduced, and the feeling of use is excellent.
〔実施例3−1〕
合成例1で得られた共重合体(1)を3質量%、低分子ヒアルロン酸(キッコーマン製、商品名「FCH−SU」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Example 3-1]
An aqueous solution containing 3% by mass of the copolymer (1) obtained in Synthesis Example 1, 0.1% by mass of low molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-SU"), and 10% by mass of glycerin was prepared. And evaluated. The results are shown in Table 3.
〔実施例3−2〕
合成例2で得られた共重合体(2)を3質量%、低分子ヒアルロン酸(キッコーマン製、商品名「FCH−SU」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Example 3-2]
An aqueous solution containing 3% by mass of the copolymer (2) obtained in Synthesis Example 2, 0.1% by mass of low molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-SU"), and 10% by mass of glycerin was prepared. And evaluated. The results are shown in Table 3.
〔実施例3−3〕
合成例1で得られた共重合体(1)を3質量%、高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Example 3-3]
An aqueous solution containing 3% by mass of the copolymer (1) obtained in Synthesis Example 1, 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200"), and 10% by mass of glycerin was prepared. And evaluated. The results are shown in Table 3.
〔実施例3−4〕
合成例2で得られた共重合体(2)を3質量%、高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Example 3-4]
An aqueous solution containing 3% by mass of the copolymer (2) obtained in Synthesis Example 2, 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200"), and 10% by mass of glycerin was prepared. And evaluated. The results are shown in Table 3.
〔比較例3−1〕
低分子ヒアルロン酸(キッコーマン製、商品名「FCH−SU」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Comparative Example 3-1]
An aqueous solution containing 0.1% by mass of low-molecular-weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-SU") and 10% by mass of glycerin was prepared and evaluated. The results are shown in Table 3.
〔比較例3−2〕
高分子ヒアルロン酸(キッコーマン製、商品名「FCH−200」)を0.1質量%、グリセリンを10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Comparative Example 3-2]
An aqueous solution containing 0.1% by mass of high molecular weight hyaluronic acid (manufactured by Kikkoman, trade name "FCH-200") and 10% by mass of glycerin was prepared and evaluated. The results are shown in Table 3.
〔比較例3−3〕
グリセリン(富士フィルム和光純薬工業、試薬)を10質量%含む水溶液を調整し、評価を行った。結果を表3に示した。
[Comparative Example 3-3]
An aqueous solution containing 10% by mass of glycerin (Fujifilm Wako Pure Chemical Industries, Ltd., reagent) was prepared and evaluated. The results are shown in Table 3.
本発明の保湿剤用ポリマーは、保湿剤、皮膚化粧料、皮膚外用剤、頭髪化粧料などに有用である。
The polymer for moisturizer of the present invention is useful for moisturizers, skin cosmetics, skin external preparations, hair cosmetics and the like.
Claims (10)
重量平均分子量が80000以上である、
保湿剤用ポリマー。
Weight average molecular weight is 80,000 or more,
Moisturizer polymer.
A skin cosmetic, an external preparation for skin, or a hair cosmetic containing the polymer for moisturizer according to any one of claims 1 to 6.
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